Machine learning and statistical analysis for catalyst structure prediction and design

Abstract

Disclosed herein are transition state models of heteroatom ligand-metal compound complexes developed for activity, purity, and / or selectivity for the selective oligomerization of ethylene, as well as density functional theory calculations for determining the reactivity, product purity, and / or selectivity of heteroatom ligand-metal compound complexes for ethylene trimerization and / or tetramerization. Using the ground and transition states of the reaction in combination with a ground and transition state and / or energy span model, the present disclosure reveals that multiple ground and transition states exist in the chromium chromacycle mechanism, which may explain the activity, purity, and / or selectivity for the selective oligomerization of ethylene. Based on the ground and transition states of the reaction in combination with a ground and transition state and / or energy span model, the methods disclosed herein can be used qualitatively and semi-quantitatively to predict the relative activity, purity, and / or selectivity of heteroatom ligand-metal compound complexes, leading to a successful process for catalyst design and implementation in which new ligands can be successfully identified and experimentally validated.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 037,405, filed June 10, 2020, which is incorporated herein by reference in its entirety.

[0002] The present disclosure relates to computational methods for developing new catalytic systems, including chromium-based catalytic systems for the selective conversion of ethylene to alpha-olefins. [Background technology]

[0003] The selective oligomerization of ethylene can produce short-chain linear α-olefins (LAOs), which are used in the production of plasticizers, lubricants, detergents, and linear low-density polyethylene. Chromium-based complexes (e.g., (Cr)-phosphine molecular catalysts) have emerged as well-suited for large-scale industrial use. The reactivity (used synonymously herein with activity) of chromium complexes is highly dependent on the exact ligands (e.g., phosphine ligands) coordinated to the Cr. However, no simple set of empirical parameters or design principles currently exists that allows for the reliable prediction of chromium complexes with high activity, high product purity, and / or high selectivity for ethylene trimerization and / or tetramerization. Furthermore, a general strategy for the computational design of homogeneous molecular catalysts remains elusive.

[0004] Therefore, there remains a need for new methods, including new computational methods, for the design and development of chromium complexes for the oligomerization of ethylene that have improved activity, improved product purity, and / or improved selectivity for 1-hexene and / or 1-octene production. There also exists a need for new computational methods that can be experimentally validated to better design new chromium-based complexes for the selective oligomerization of ethylene, specifically to increase catalyst activity / productivity, increase product purity, and / or increase 1-octene selectivity. Summary of the Invention

[0005] The present disclosure provides new methods for the design and development of ethylene oligomerization catalysts with improved activity / productivity, selectivity to 1-hexene or 1-octene, and / or product purity (e.g., 1-hexene product purity and / or 1-octene product purity). The methods provided herein can be experimentally validated and iteratively enhanced to design and improve new heteroatom ligand-metal compound complexes for the selective oligomerization of ethylene, including increasing 1-octene selectivity, among other properties. Heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes, such as the Cr N-phosphine amidine (Cr(P,N)) or ((P,N)Cr) catalysts described herein) have been investigated and designed using transition state models with activity / productivity, product purity, and / or selectivity calculated by various methods.

[0006] Heteroatomic ligand-metal compound complexes (e.g., heteroatomic ligand-chromium compound complexes such as Cr N-phosphine amidine (Cr(P,N)) complexes, among others disclosed herein) can provide high selectivity (approximately 99%) for 1-hexene. In designing new heteroatomic ligand-metal compound complexes (e.g., heteroatomic ligand-chromium compound complexes) with increased activity / productivity, increased product purity, and / or that are more selective for 1-hexene and / or 1-octene, the design process can involve an iterative process of identifying and adjusting key structural or electronic features of "training" (also referred to as "educational") heteroatomic ligand-metal compound complexes (e.g., heteroatomic ligand-chromium compound complexes such as Cr N-phosphine amidine (Cr(P,N)) complexes, among others disclosed herein) that affect the relative energies of the ground and transition states, which affect productivity, product purity, and / or 1-octene and / or 1-hexene selectivity. The same design process can also be used to improve the selectivity of the trimerization catalytic cycle to 1-hexene (also referred to as trimerization cycle selectivity to 1-hexene), the selectivity of the tetramerization catalytic cycle to 1-octene, and / or the 1-octene efficiency of the fourth ethylene addition. These key structural or electronic features can be used as input variables for the development of a computational design that explores the relative energies of the ground and transition states and, therefore, their relative importance in affecting the overall activity / productivity, purity, and / or selectivity of the oligomerization process. Based on this computational design, "target" heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes, such as Cr(P,N) complexes, among others disclosed herein) can be identified according to the desired adjustment of structural or electronic features, and these target complexes can be synthesized and experimentally validated. Based on these results, computational redesign or iteration can be used to identify next-generation target complexes, which can also be experimentally validated and subjected to further testing and redesign.In this manner, the performance of heteroatom ligand-metal compound complexes (eg, heteroatom ligand-chromium compound complexes) can be predicted and improved.

[0007] For example, in certain embodiments, transition state models of heteroatomic ligand-metal compound complexes (e.g., heteroatomic ligand-chromium compound complexes such as Cr N-phosphine amidine complexes, among others disclosed herein) have been developed for activity / productivity, product purity, and / or selectivity, and density functional theory calculations can be used to address the activity / productivity, product purity, and / or reactivity of the complexes toward ethylene trimerization and tetramerization. Using ground and transition states and / or ground and transition states in combination with energy span models, the present disclosure demonstrates that mechanisms involving metallocyclic intermediates can be utilized to predict the activity / productivity, product purity, and / or selectivity of heteroatomic ligand-metal compound complexes. For example, in non-limiting embodiments, heteroatomic ligand-chromium compound complexes can be developed for activity / productivity, product purity, and / or selectivity of Cr N-phosphine amidine complexes. I High-spin Cr I / IIIThe chromacycle mechanism can be utilized to predict and / or estimate the activity / productivity, product purity, and / or selectivity factors of heteroatomic ligand-metal compound complexes. Based on the calculated energy landscape, the calculated activity / productivity, product purity, and / or selectivity of the heteroatomic ligand-metal compound complex can be correlated to experimental values, and this correlation can be used to predict the activity / productivity, product purity, and / or selectivity of new complex heteroatomic ligand-metal compound complexes. Thus, this analysis can calculate and compare the activity / productivity, product purity, and / or selectivity of other heteroatomic ligand-metal compound complexes. Based on the catalytic energy span of heteroatomic ligand-metal compound complexes, the calculations disclosed herein can qualitatively and semi-quantitatively reproduce the relative activity / productivity, product / purity, and / or selectivity of heteroatomic ligand-chromium compound complexes, and can lead to a successful process for the design and implementation of heteroatomic ligand-metal compound complexes (e.g., heteroatomic ligand-chromium compound complexes) in which new heteroatomic ligands can be successfully identified and experimentally validated.

[0008] In particular, the present disclosure provides a method for designing heteroatom ligand-metal compound complexes for the oligomerization of olefins that identifies and explores several possible ground and transition states in the oligomerization process, including ground states that traverse different transition states to the desired oligomer product (e.g., olefin trimer and / or olefin tetramer versus other olefin oligomerization products). This method allows for the identification of important structural and electronic features of the identified ground and transition states that affect activity / productivity, product purity, and / or selectivity, and provides information on how to tune these features in next-generation designs to improve activity / productivity, product purity, and selectivity.

[0009] In some embodiments, the heteroatom ligand-metal compound complex has the general formula [(HetLig)CrX q L r ]3-q (A) where HetLig represents a training heteroatom ligand that can be investigated and adjusted to change the electronic and / or structural features of the ligand, X is an anionic ligand, q is an integer, L is a neutral ligand, r is an integer, and any two or more of the X and L ligands may be linked to form a multidentate ligand. This disclosure explores the detailed characteristics of heteroatom ligands and their complexes with metal compounds (e.g., chromium compounds) and how such characteristics affect the ground and transition state energies.

[0010] Thus, in one aspect, the present disclosure provides a method for designing heteroatom ligand-metal compound complexes for olefin oligomerization, the method comprising: (a) n input variables I 1 , I 2 , …I n (n is an integer), and each input variable is selected from one or more ground state model structures GS A1 , …GS Ap (p is an integer), and a plurality of transition state model structures TS associated with the one or more ground state model structures. A1 , T.S. A2 , …TS Am (m is an integer), the one or more ground state model structures GS A1 , …GS Ap and each of the plurality of transition state model structures TS A1 , T.S. A2 , …TS Am are derived from one or more first training heteroatom ligand-metal compound complexes, each complex comprising a first training heteroatom ligand; (b) The ground state model structure GS A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS AmFor each of the n input variables I 1 , I 2 , …I n assigning a quantitative value to (c) generating, by at least one processor of the device, the ground state model structure G.S. A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS Am determining the relative energies of each of (d) For each n input variables I 1 , I 2 , …I n The quantitative value of and the ground state model structure GS A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS Am generating a machine learning model based on the correlation of each of the relative energies of (e) Based on the machine learning model, [1] the ground state model structure GS A1 , …GS Ap and one of the plurality of transition state model structures TS A1 , T.S. A2 , …TS Am [2] the difference in energy between at least one of the transition state model structures TS [ΔG(TS-GS) or ΔΔG(TS-GS)] A1 , T.S. A2 , …TS Am The n input variables I are associated with the energy difference [ΔG(TS-TS) or ΔΔG(TS-TS)] between any two or more of 1 , I 2 , …I n and identifying one or more of: (f) the one or more n input variables I identified from step (e). 1 , I 2 , …I nand generating first target heteroatom ligand-metal compound complexes for olefin oligomerization, each of the first target heteroatom ligand-metal compound complexes having one or more ground state model structures GS B1 , …GS Bx (x is an integer), or a plurality of transition state model structures TS associated with said one or more ground state model structures. B1 , T.S. B2 , …TS By n output variables O having quantitative values ​​corresponding to any of the structural or electronic properties of 1 , O 2 , …O n is characterized by the one or more ground state model structures GS B1 , …GS Bx and each of the plurality of transition state model structures TS B1 , T.S. B2 , …TS By are derived from the first target heteroatom ligand-metal compound complex, each complex comprising a first target heteroatom ligand; (g) identifying one or more performance parameters associated with an olefin oligomerization reaction and values ​​of the performance parameters for the one or more first training heteroatom ligand-metal compound complexes and the first target heteroatom ligand-metal compound complex; (h) the n output variables O of the first target heteroatom ligand-metal compound complex 1 , O 2 , …O n The quantitative value of is calculated based on n new input variables I derived from one or more second training heteroatom ligand-metal compound complexes containing the second training heteroatom ligand for olefin oligomerization. 1.1 , I 2.1 , …I n.1repeating steps (a)-(f) one or more times using as an input data set n of n, n = 1, n = 2, n = 3, n = 4, n = 5, n = 6, n = 7, n = 8, n = 9, n = 10, n = 11, n = 12, n = 13, n = 14, n = 15, n = 16, n = 17, n = 18, n = 19, n = 20, n = 21, n = 22, n = 23, n = 24, n = 25, n = 26, n = 27, n = 28, n = 29, n = 30, n = 31, n = 32, n = 33, n = 40, n = 41, n = 42, n = 43, n = 44, n = 45, n = 46, n = 47, n = 48, n = 50, n = 51, n = 52, n = 53, n = 54, n = 55, n = 56, n = 57, n = 58, n = 59, n = 60, n = 61, n = 62, n = 63, n = 64, n = 65, n = 66, n = 67, n = 68, n = 69, n = 70, n = 71, n = 72, n = 73, n = 74, n = 75, n = 76, n = 77, n = 78, n = 79, n = 80, n = 81, n = 82, n = 83, n = 84, n = 85, n = 86, n = 87, n = 88, n = 89, n = 9 1.1 , O 2.1 , …O n.1 and a performance parameter value of one or more second target heteroatom ligand-metal compound complexes; Includes.

[0011] In this embodiment, the ground state model structure GS A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS Am For each of the n input variables I 1 , I 2 , …I n In step (b), the assigned quantitative values ​​may be independently assigned raw values ​​or normalized values. Also in this embodiment, the ground state model structure G.S. is calculated by at least one processor of the device. A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS Am In step (c), the relative energies of each of the above-described structures are determined. These determined relative energies can independently be the relative energies of a possible ensemble of conformations of the ground state model structure and the transition state model structure or one specific conformation.

[0012] In this embodiment, further in step (d), the machine learning model of step (e) is 1 , I 2 , …I n Quantitative values ​​of and the ground state model structure GS A1 , …GSAp and the transition state model structure TS A1 , T.S. A2 , …TS Am In this way, the relative energy of each of the n input variables I 1 , I 2 , …I n and the ground state model structure GS A1 , …GS Ap There may be a relationship between the relative energies of each n input variable I 1 , I 2 , …I n and the transition state model structure TS A1 , T.S. A2 , …TS Am There may be a relationship between the relative energies of the n input variables I 1 , I 2 , …I n Some of these are shown as examples in FIG.

[0013] In this embodiment, furthermore, in step (e), the relationship in step (d) is 1 , I 2 , …I n [1] Ground state model structure GS A1 , …GS Ap and multiple transition state model structures TS A1 , T.S. A2 , …TS Am [2] a difference in energy between at least one of the transition state model structures TS [ΔG(TS-GS) or ΔΔG(TS-GS)] A1 , T.S. A2 , …TS Am In particular, n input variables I associated with [1] ΔG(TS-GS) or ΔΔG(TS-GS) or [2] ΔG(TS-TS) or ΔΔG(TS-TS) may be used. 1 , I 2 , …I nIn identifying one or more of these ΔG or ΔΔG energy differences, these ΔG or ΔΔG energy differences can be based on Boltzmann ensemble ΔG or ΔΔG values.

[0014] Further to this aspect, the machine learning model of steps (d), (e), and (h) may comprise one or more neural networks. The machine learning model may be iteratively applied to identify and tune key structural or electronic features of the heteroatom ligand-metal compound complex that affect the relative energies of the ground and transition states with respect to activity / productivity, selectivity (1-octene vs. 1-hexene production), and product purity (1-hexene vs. other C6 products and / or 1-octene vs. other C8 products). These key structural or electronic features may be fed into the machine learning model as n input variables I 1 , I 2 , …I n Using the above equations, machine learning models can be trained to investigate the relative energies of the ground and transition states, and therefore their relative importance in affecting the overall activity / productivity, product purity, and selectivity of the oligomerization process. In this manner, machine learning models can be trained to assess the effect that structural or electronic features may have on the relative energies of the ground and transition states, and therefore the overall activity / productivity, product purity, and selectivity of the oligomerization process. Based on this computational design, "target" heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes) can be identified according to the desired adjustments in structural or electronic features, and these target complexes can be synthesized and experimentally validated. Based on these results, computational redesign or iteration can be used to identify next-generation target complexes, which can also be experimentally validated and subjected to further testing and redesign of the machine learning model.

[0015] Further to this aspect, step (f) may use the mapping generated by step (e) as input to generate an output comprising first target heteroatom ligand-metal compound complexes for olefin oligomerization, each of which comprises a first target heteroatom ligand, wherein the first target heteroatom ligand-metal compound complexes each have one or more ground state model structures G.S. B1 , …GS Bx (x is an integer), or a plurality of transition state model structures TS associated with one or more ground state model structures. B1 , T.S. B2 , …TS By n output variables O having quantitative values ​​corresponding to any of the structural or electronic properties of 1 , O 2 , …O n One or more ground state model structures GS B1 , …GS Bx Each of the transition state model structures TS B1 , T.S. B2 , …TS By are generated from a first target heteroatom ligand-metal compound complex, each complex containing a first target heteroatom ligand. In this way, n output variables O 1 , O 2 , …O n is the number of new n input variables I 1.1 , I 2.1 , …I n.1 to evaluate the input variables with respect to their respective effects on the relative energies of the ground and transition states.

[0016] Further to this aspect, step (h) may further comprise: generating n output variables O of the first target heteroatom ligand-metal compound complex; 1 , O 2 , …O n The quantitative value of is calculated based on n new input variables I derived from one or more second training heteroatom ligand-metal compound complexes containing the second training heteroatom ligand for olefin oligomerization. 1.1, I 2.1 , …I n.1 , new n input variables I 1.1 , I 2.1 , …I n.1 The method may involve one or more iterative repetitions of steps (a)-(f) using as an input data set of n new output variables O, which is input to a machine learning model to generate a second target heteroatom ligand-metal compound complex comprising the second target heteroatom ligand, wherein the second target heteroatom ligand-metal compound complex generates new n new output variables O. 1.1 , O 2.1 , …O n.1 and performance parameter values ​​of one or more second target heteroatom ligand-metal compound complexes. In this way, the machine learning model may continue to learn which structural or electronic features of heteroatom ligand-metal compound complexes affect the relative energies of the ground and transition states in order to identify target heteroatom ligand-metal compound complexes.

[0017] In further addition to this aspect, the disclosed method comprises: (i) [1] synthesizing a first target heteroatom ligand and / or a second target heteroatom ligand, or [2] synthesizing a first target heteroatom ligand and / or a second target heteroatom ligand, followed by synthesizing a first target heteroatom ligand-metal compound complex or a second target heteroatom ligand-metal compound complex. It may further include:

[0018] Also in this aspect, the disclosed method also includes: (j) performing an olefin oligomerization reaction by [1] contacting a first target heteroatom ligand or a second target heteroatom ligand, a metal compound, an organometallic compound, and an olefin, or [2] contacting a first target heteroatom ligand-metal compound complex or a second target heteroatom ligand-metal compound complex, an organometallic compound, and an olefin. It may further include:

[0019] These and other embodiments and aspects of these processes, methods, and compositions, including catalyst compositions, are more fully described in the detailed description and claims, as well as in the further disclosure, such as the examples, provided herein. [Brief explanation of the drawings]

[0020] [Figure 1] 1 illustrates some of the geometric input variables used in accordance with aspects of the method of the present disclosure. [Figure 2A] Examples of descriptors extracted for machine learning analysis aspects include: providing geometric descriptors and electrostatic charges; [Figure 2B] The following are exemplary descriptors extracted for machine learning analysis aspects: Illustrates the definition of percent buried volume. [Figure 2C] The following are examples of descriptors extracted for machine learning analysis aspects: A definition of distance from pocket is shown. [Figure 3] 1-Hexene rotational frequency reaction schemes are illustrated showing various ground and transition states, as well as illustrating the transition state energy barriers that can contribute to 1-hexene rotational frequency and therefore productivity. [Figure 4] 1-octene turnover frequency starting from GS-VI, which may contribute to the activity / productivity.

[0039] Figure 3 illustrates the ground and transition states and transition state energy barriers, in addition to those illustrated in Figure 3, that may be required for the 1-octene turnover frequency reaction scheme starting from GS-VI. [Figure 5A] FIG. 1 illustrates one embodiment of the present disclosure, showing catalytic cycle pathways in which 1-hexene and / or 1-octene are accessible from a common ground state and can be used to calculate C6 / C8 selectivity. [Figure 5B]FIG. 1 illustrates another embodiment of the present disclosure, showing catalytic cycle pathways by which 1-hexene and / or 1-octene can propagate through a trimerization and / or tetramerization catalytic cycle to produce branched decene, branched dodecene, and / or branched tetradecene. [Figure 5C]

[0023] Figure 1 illustrates a further embodiment of the present disclosure showing catalytic cycle pathways by which 1-hexene and / or 1-octene can propagate through a trimerization and / or tetramerization catalytic cycle to produce branched decene, branched dodecene, and / or branched tetradecene. [Figure 6] Illustrates pathways by which 1-hexene can be formed and by which a six-carbon impurity can arise in the production of 1-hexene. [Figure 7] This illustrates the energy differences of transition state (TS) ensembles that can control the pathway to 1-hexene and to other C compounds that may be impurities in the isolated 1-hexene product. [Figure 8] A comparison of the experimentally reported ethylene trimerization of heteroatom ligand-chromium compound complexes and their productivity in g 1-C6 / g Cr h for the ligands used is shown. The mass percentage of 1-hexene out of the total mass of C6 product is given in parentheses. [Figure 9A] Simplified Gibbs free energy landscapes are provided for ethylene trimerization using two different heteroatom ligands (i.e., (P,N)Cr 1a and (P,N,P)Cr 8a) in heteroatom ligand-chromium compound complexes, where the ligands are represented by HetLig. Intermediates GS-I and GS-II for catalyst 1a are sextet spins, while all other intermediates and transition states are quartet spins. The numbers in parentheses represent the relative contribution of the structure to the rotational frequency of the heteroatom ligand-chromium compound complex, relative to the ground state or transition state. [Figure 9B] Gibbs free energy values ​​in kcal / mol are shown for the ground and transition states of the ethylene trimerization catalytic cycle for heteroatom ligand-chromium compound complexes using ligands 2 to 7. [Figure 10]Illustrated are 3D representations of key intermediates and transition states for catalysts 1a and 8a, with some atoms removed for clarity. [Figure 11] Figure 1 illustrates the Gibbs free energy surface for ethylene trimerization over catalyst 1a. The solid surface is the simplified Gibbs free energy surface for ethylene trimerization over catalyst 1a at 50 bar ethylene pressure using M06-L, and the dotted surface is the Gibbs free energy landscape (kcal / mol) over ωB97X-D. [Figure 12] A plot of the natural logarithm of the experimental productivity values ​​(g 1-C6 / g Cr·h) corrected for 1-hexene alone versus the natural logarithm of the calculated 1-C6 productivity values ​​is shown. Productivity of 8a was evaluated as the natural logarithm of unity. [Figure 13A] This paper outlines the reaction conditions for the selective oligomerization of ethylene targeting 1-hexene and 1-octene using a heteroatom ligand-chromium compound complex catalyst, "Cr(P,N)," which has coordination of phosphine and imine ligands. Modified methylaluminoxane (MMAO) is typically used to activate the precatalyst complex. [Figure 13B] To demonstrate the transition state selectivity model used in this disclosure, a computational study was conducted to investigate the cationic high-spin transition states TS-III (leading to 1-hexene) and TS-IV (leading to 1-octene) in order to develop a linear correlation model between DFT calculations and the experimental 1-hexene:1-octene ratio. [Figure 13C] The disclosed workflow for combining transition states and machine learning is illustrated using the 1-hexene / 1-octene transition state selectivity model disclosed herein. By combining the transition state with the machine learning model, selectivity-controlling features can be discovered, which are then used for the virtual design of new catalyst ligands. [Figure 14]This section provides an overview of 105 unique heteroatom-ligand-chromium compound complexes, "Cr(P,N)" ligands, with phosphine and imine ligand coordination in a training or teaching dataset of transition states, each of which has a variety of different functional groups but retains the coordination of phosphine and imine or imine-like ligands, for which DFT transition state models were developed. [Figure 15] Figure 1 illustrates the root mean square error (RMSE) for machine learning regression algorithms for quantitatively predicting the energy difference between TS-III and TS-IV using 14 atomic and molecular features. In this figure, RF = Random Forest, LASSO = Least Absolute Value Shrinkage Selection Operator, GPR = Gaussian Process Regression, and SVR = Support Vector Regression. [Figure 16A] Linear regression of selectivity predicted by the DFT selectivity model (x-axis) and the optimized random forest (RF) model (y-axis) is shown, with negative values ​​corresponding to high 1-hexene selectivity and positive values ​​corresponding to high 1-octene selectivity. [Figure 16B] 1 provides linear regression of 1-octene selectivity predicted by the DFT selectivity model (circles) and the optimized random forest (RF) model (triangles) compared to experimental values. [Figure 17] The average predicted selectivity from machine learning (red) is compared with the selectivity from DFT calculations. [Figure 18] Normalized feature importance determined from the random forest model is illustrated with 95% confidence intervals (red bars). Distance Poc is the distance from the pocket, volume Bur is the percent buried volume, and other parameters are shown in Figures 1 and 2A. [Figure 19A] Example structures are shown for previous generation (P,N) ligands and new proposed ligands (third generation) based on features identified by machine learning. Predicted 1-hexene:1-octene selectivity is given below each structure. [Figure 19B]1-Octene selectivity is plotted for previous generation heteroatom ligand-chromium compound complexes with coordination of phosphine and imine ligands, "Cr(P,N) ligands," and the new generation heteroatom ligands developed in this disclosure. [Figure 20] Illustrated are competing, selectivity-determining reaction coordinate pathways for producing hexene and octene, including the general N2-phosphinylamidine chromacycloheptane complexes CrCH1 and CrCH2, as well as the hexene transition state TS C6 of the general N2-phosphinylamidine chromium salt complex, and the octene transition state TS C8 of the general N2-phosphinylamidine chromium salt complex. [Figure 21A] Figure 1 illustrates the Gibbs free energy landscape of a deprotonated NH N-phosphinyl amidine ligand and a globally neutral Cr catalyst complex with a CrI / III cycle. Energies are shown in kcal / mol. The ground states GS-I and GS-II have a sextet spin state as the lower energy, and all other ground and transition states have a quadruplet spin state as the lowest energy. The ground states GS-I and GS-II have a sextet spin state as the lowest energy, and all other ground and transition states have a quadruplet spin state as the lowest energy. [Figure 21B] Gibbs free energy landscapes of deprotonated NH N-phosphinyl amidine ligands and overall cationic Cr complexes with Cr II / IV cycles are shown. Energies are given in kcal / mol. Ground states GS-I and GS-II have a quintet spin state as the lowest energy, and all other ground states have a triplet spin state as the lowest energy. [Figure 22] Gibbs free energy landscapes (kcal / mol) for N-dimethylaluminum-substituted models, specifically 1c-AlMe2 catalyst, for the cationic CrI / III reaction channel are shown. The ground states GS-I and GS-II have sextet spin states as their lowest energies, and all other ground and transition states have quartet spin states as their lowest energies. [Figure 23] Relative energies for all ethylene coordination structures and alternative mechanistic pathways involving coordinated ethylene are illustrated (energies in kcal / mol). [Figure 24] The enthalpy, Gibbs free energy, and entropy-normalized Gibbs free energy surface (ΔGS,corr) of the ground state GS-II to GX-VI with the transition states TS-I and TS-II are compared. [Figure 25] Kinetic experiments were performed at high ethylene pressure (50 bar). The Gibbs free energy surface of 1a is illustrated by the ωB97X-D with ethylene pressure correction relative to the calculated Gibbs free energy surface. [Figure 26] The Gibbs free energy surface of amine-dissociated ligand 8c is shown (energies in kcal / mol). Ground states GS-I and GS-II have sextet spin states as their lowest energies, and all other ground and transition states have quartet spin states as their lowest energies. [Figure 27] Illustrated is the spin crossover shown to provide a lower energy pathway from the ground state GS-II (sextet spin state as lowest energy) of bis(ethylene)-coordinated Cr to the transition state TS-I, with the spin states indicated in parentheses (energies in kcal / mol). [Figure 28A] The calculated free energy landscape for the "truncated" model 1b is shown (energies in kcal / mol). [Figure 28B] The calculated free energy landscape for the "truncated" model 8b is shown (energies in kcal / mol). [Figure 29A] Figure 29A illustrates the Gibbs free energy surfaces for chromium complexes containing Ligand 2 at 298 K and 1 atm pressure using the solvents listed in Table S1. Thus, the surface in Figure 29A is for the Ligand 2 complex. [Figure 29B]Figure 29B illustrates the Gibbs free energy surface for chromium complexes containing Ligand 3 at 298 K and 1 atm pressure using the solvents listed in Table S1. Thus, the surface in Figure 29B is for the Ligand 3 complex. [Figure 29C] Figure 29C illustrates the Gibbs free energy surface for chromium complexes containing Ligand 4 at 298 K and 1 atm pressure using the solvents listed in Table S1. Thus, the surface in Figure 29C is for the Ligand 4 complex. [Figure 29D] Figure 29D illustrates the Gibbs free energy surface for chromium complexes containing Ligand 5 at 298 K and 1 atm pressure using the solvents listed in Table S1. Thus, the surface in Figure 29D is for the Ligand 5 complex. [Figure 29E] Figure 29E illustrates the Gibbs free energy surface for chromium complexes containing Ligand 6 at 298 K and 1 atm pressure using the solvents listed in Table S1. Thus, the surface in Figure 29E is for the Ligand 6 complex. [Figure 29F] Figure 29F illustrates the Gibbs free energy surface for chromium complexes containing ligand 7 at 298 K and 1 atm pressure using the solvents listed in Table S1. Thus, the surface in Figure 29F is for the ligand 7 complex. [Figure 30] The energy landscape for catalyst 1a by MO6L is shown. The free energy barrier of 6–15 kcal / mol is consistent with the experimental reaction temperatures. [Figure 31] Illustrated are possible conformations of transition states TS-III and TS-IV for exemplary heteroatom ligand-chromium compound complexes, i.e., the conformational changes that result in unique transition state geometries. [Figure 32] Illustrated are 3D structures of the bottom 20 transition state conformations of the TS-III ensemble for exemplary heteroatom ligand-chromium compound complexes, with relative free energies in kcal / mol. [Figure 33] Illustrated are 3D structures of the bottom 20 transition state conformations of the TS-IV ensemble for exemplary heteroatom ligand-chromium compound complexes, with relative free energies in kcal / mol. [Figure 34] A linear correlation plot using the Boltzmann distribution is provided that includes the ensemble of all calculated transition states for TS-III and TS-IV using the indicated ligands. [Figure 35] FIG. 1 illustrates a schematic of the machine learning model used to generate target heteroatom ligand-metal compound complexes. DETAILED DESCRIPTION OF THE INVENTION

[0021] Among other things, the present disclosure provides methods for determining and modifying the reactivity (activity / productivity), product purity, and / or selectivity of ethylene oligomerization catalyst systems based on heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes). The methods include methods aimed at increasing the activity / productivity, the proportion of 1-octene or 1-hexene in the product, and / or increasing the 1-olefin content of the C6 and / or C8 oligomerization products. The methods also include methods aimed at decreasing the proportion of by-products produced. It has been found that density functional theory (DFT) calculations can be used to address activity / productivity, product purity, and / or selectivity for the selective oligomerization of ethylene using transition state models of heteroatom ligand-metal compound complexes. This aspect of the disclosure demonstrates the use of ground and transition states in combination with ground and transition state and / or energy span models to enable the discovery of empirical parameters or design principles that provide predictions of high activity / productivity, product purity, and / or product selectivity for heteroatom ligand-metal compound complexes.

[0022] In certain embodiments, it is also demonstrated herein that by combining machine learning computational methods with quantum mechanical transition state models, it is possible to identify specific design features for the selective oligomerization of olefins using heteroatom ligand-metal compound complexes. No useful general strategies for hypothetical catalyst design or improvement have been developed, and it is difficult to identify simple chemical features that control ethylene oligomerization catalysis, where small energy differences can have significant effects. In one embodiment, the present disclosure provides the development of density functional theory (DFT) transition state models in combination with a heteroatom ligand-metal compound complex design workflow that combines quantum mechanical transition state modeling with machine learning to identify design features for specific heteroatom ligand-chromium compound complexes targeted at the production of 1-hexene and / or 1-octene.

[0023] definition In order to more clearly define the terms used herein, the following definitions are provided, and these definitions are applicable throughout this disclosure unless otherwise indicated or the context requires otherwise. When a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Chemical Terminology, Second Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein or is not held to be unclear or invalid in any claim to which the definition applies. To the extent that any definition or usage provided by any document incorporated by reference herein conflicts with the definition or usage provided herein, the definition or usage provided herein shall control.

[0024] With respect to transitional words or phrases in a claim, the transitional term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consisting essentially of" limits the scope of the claim to the specified materials or steps and those that do not materially affect the basic and novel feature(s) of the claimed invention. "Consisting essentially of" claims occupy a middle ground between closed-form claims written in the "consisting of" format and fully open-form claims written in the "comprising" format. Unless specified to the contrary, a description of a compound or composition "consisting essentially of" should not be construed as "comprising," but rather is intended to describe the stated components, including materials that do not significantly alter the composition or method to which the term is applied. For example, a feedstock consisting essentially of material A may contain impurities typically present in commercially produced or commercially available samples of the recited compound or composition. When a claim includes different features and / or classes of features (e.g., process steps, feedstock features, and / or product features, among other possibilities), the transitional terms comprising, consisting essentially of, and consisting of apply only to the class of features to which they are applied, and different transitional words or phrases may be used for different features within the claim. For example, a method may include several recited steps (and other unrecited steps), but may utilize the preparation of a catalyst composition consisting of certain steps, but may utilize a catalyst composition that includes recited components and other unrecited components. While compositions, processes, and computational methods are described in terms “comprising” various components or steps, these compositions, processes, and computational methods may also “consist essentially of” or “consist of” the various components or steps.

[0025] The terms "a," "an," and "the" are intended to include plural alternatives (e.g., at least one) unless clearly indicated otherwise. For example, disclosure of "an organoaluminum compound" is intended to encompass one organoaluminum compound, or a mixture or combination of more than one organoaluminum compound, unless expressly stated otherwise.

[0026] With respect to any specific compound disclosed herein, the provided general structure or name is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that may arise from a particular set of substituents, unless otherwise indicated. Thus, a general reference to a compound includes all structural isomers unless otherwise explicitly indicated; for example, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while a general reference to a butyl group includes n-butyl, sec-butyl, iso-butyl, and tert-butyl. Furthermore, a reference to a general structure or name encompasses all enantiomers, diastereomers, and other optical isomers, whether enantiomeric or racemic, as well as mixtures of stereoisomers, as permitted or required by the context. With respect to any specific formula or name provided, the provided general formula or name also encompasses all conformational isomers, positional isomers, and stereoisomers that may arise from a particular set of substituents.

[0027] Unless otherwise specified, any carbon-containing group in which the number of carbon atoms is not specified can have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms, or any range or combination of ranges therebetween, in accordance with appropriate chemical conventions. For example, unless otherwise specified or unless the context requires otherwise, any carbon-containing group can have 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms, etc. In certain embodiments, the context may require other ranges or limitations, such as when the carbon-containing group in question is an aryl or alkenyl group, and the lower limits for carbon atoms in these groups in question are 6 carbon atoms and 2 carbon atoms, respectively. Additionally, other identifiers or qualifying terms may be utilized, such as to indicate the presence or absence of particular substituents, particular regiochemistry and / or stereochemistry, or the presence or absence of branched substructures or backbones.

[0028] Various numerical ranges are disclosed herein. When an applicant discloses or claims any type of range, unless otherwise specified, the applicant's intention is to individually disclose or claim each possible number that such range can reasonably encompass, including the endpoints of the range and any subranges and combinations of subranges subsumed therein. For example, by disclosing that a bond angle may be from 90° to 100°, the applicant's intention is to individually recite 90°, 91°, 92°, 93°, 94°, 95°, 96°, 99°, 98°, 99°, and 100°, including any subranges and combinations of subranges subsumed therein, and these methods of describing such ranges are interchangeable. Moreover, all numerical endpoints of ranges disclosed herein are approximations unless excluded by disclaimer. As a representative example, if applicant states that one or more steps in a process disclosed herein may be carried out at a temperature in the range of 10°C to 75°C, this range should be interpreted as encompassing temperatures in the range of "about" 10°C to "about" 75°C.

[0029] Values ​​or ranges may be expressed herein as "about," "from about" one particular value, and / or to "about" another particular value. When such values ​​or ranges are expressed, other disclosed embodiments include the specific value stated, from the one particular value, and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that there are several values ​​disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. In other aspects, use of the term "about" can mean ±15% of the specified value, ±10% of the specified value, ±5% of the specified value, or ±3% of the specified value.

[0030] If applicant chooses to claim less than the full range of the present disclosure for any reason, for example, to take into account references that applicant may not know at the time of filing this application, applicant reserves the right to disclaim or exclude any individual member of any such group of values ​​or ranges, including any subrange or combination of subranges within that group, that may be claimed according to range or in any similar manner. Further, if applicant chooses to claim less than the full range of the present disclosure for any reason, for example, to take into account references or prior disclosures that applicant may not know at the time of filing this application, applicant reserves the right to disclaim or exclude any individual substituent, analog, compound, ligand, structure, or group thereof, or any member of a claimed group.

[0031] The term "substituted," when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in the group and is intended to be open-ended. Group(s) may also be referred to herein as "unsubstituted" or by equivalent terms such as "non-substituted," which refers to the original group in which a non-hydrogen moiety has not replaced a hydrogen in the group. Unless otherwise specified, "substituted" is intended to be open-ended and to include inorganic or organic substituents as would be understood by one of ordinary skill in the art.

[0032] Specific chemical groups, such as "oxygen-binding groups" (also called "oxygen radicals"), may be specified according to the atom that is bonded to the metal or to another chemical moiety as a substituent. For example, oxygen-binding groups include species such as hydrocarbyloxides (-OR, where R is a hydrocarbyl group, also known as hydrocarboxy), alkoxides (-OR, where R is an alkyl group), aryloxides (-OAr, where Ar is an aryl group), or substituted analogs thereof, which function as ligands or substituents at the specified position. Thus, alkoxide and aryloxide groups are each subgenus of hydrocarbyloxide (hydrocarbyloxy) groups. Similar definitions apply to chemical groups that may be specified according to the atom that is bonded to the metal or to another chemical moiety as a substituent, such as "sulfur radicals," "nitrogen radicals," "phosphorus radicals," "arsenic radicals," "silicon radicals," "germanium radicals," "tin radicals," "lead radicals," "boron radicals," "aluminum radicals," etc., where the free valence is located on a heteroatom (non-carbon atom).

[0033] Chemical "groups" may also be described according to how they are formally derived from a reference or "parent" compound, e.g., according to the number of hydrogen atoms formally removed from the parent compound to create the group (even if the group is not literally synthesized in this manner). These groups may be utilized as substituents or coordinated to or attached to metal atoms. For example, an "alkyl group" may be formally derived by removing one hydrogen atom from an alkane, while an "alkanediyl group" (also known as an "alkylene group") may be formally derived by removing two hydrogen atoms from an alkane. Moreover, more general terms (in this example, "alkyl group" may be described as an "alkane group," which includes "alkanediyl group," "alkanediyl group," and materials with three or more hydrogen atoms removed from an alkane, as the context requires) may be used to encompass a variety of groups formally derived by removing any number ("one or more") of hydrogen atoms from a parent compound. Disclosure that a substituent, ligand, or other chemical moiety may constitute a particular "group" implies that the group, when used as described, conforms to known rules of chemical structure and bonding. When groups are described as being "derived by," "derived from," "formed by," or "formed from," such terms are used in a formal sense and are not intended to reflect any particular synthetic method or procedure, unless otherwise expressly stated or the context requires otherwise.

[0034] The term "organyl group" is used herein in accordance with the definition set forth by IUPAC: an organic substituent having one free valence at a carbon atom, regardless of the type of functional group. Similarly, an "organylene group" refers to an organic group derived from an organic compound by removing two hydrogen atoms, either from one carbon atom or from each of two different carbon atoms, regardless of the type of functional group. An "organic group" refers to a generalized group formed by removing one or more hydrogen atoms from a carbon atom of an organic compound. Thus, "organyl group," "organylene group," and "organic group" are organic groups that may contain organic functional group(s) and / or atom(s) other than carbon and hydrogen, i.e., functional groups and / or atoms other than carbon and hydrogen. For example, non-limiting examples of atoms other than carbon and hydrogen include halogens, oxygen, nitrogen, phosphorus, etc. Non-limiting examples of functional groups include ethers, aldehydes, ketones, esters, sulfides, amines, phosphines, etc. In one aspect, the hydrogen atom(s) removed to form the "organyl group," "organylene group," or "organic group" can be bonded to a carbon atom belonging to a functional group, such as an acyl group (-C(O)R), a formyl group (-C(O)H), a carboxy group (-C(O)OH), a hydrocarboxycarbonyl group (-C(O)OR), a cyano group (-C≡N), a carbamoyl group (-C(O)NH), an N-hydrocarbylcarbamoyl group (-C(O)NHR), or an N,N'-dihydrocarbylcarbamoyl group (-C(O)NR), among other possibilities. In another aspect, the hydrogen atom(s) removed to form the "organyl group," "organylene group," or "organic group" can be bonded to a carbon atom not belonging to, but separate from, a functional group, such as, for example, -CHC(O)CH, -CHNR, etc. An "organyl group," "organylene group," or "organic group" can be aliphatic, including cyclic or acyclic, or aromatic. "Organyl groups," "organylene groups," and "organic groups" also encompass heteroatom-containing rings, heteroatom-containing ring systems, heteroaromatic rings, and heteroaromatic ring systems."Organyl groups," "organylene groups," and "organic groups" can be linear or branched unless otherwise specified. Finally, it should be noted that the definition of "organyl group," "organylene group," or "organic group" includes as members "hydrocarbyl groups," "hydrocarbylene groups," "hydrocarbon groups," and "alkyl groups," "alkylene groups," and "alkane groups," respectively (among others known to those skilled in the art). When bonded to a transition metal, an "organyl group," "organylene group," or "organic group" may have the usual η. x (eta-x) nomenclature, where x is an integer corresponding to the number of atoms that are or are expected to be coordinated to the transition metal, e.g., according to the 18-electron rule.

[0035] A formamidine group has the general structure [ka] In the formamidine group, the nitrogen atom participating in the double bond with the central carbon atom is N 1 The nitrogen atom that is involved in a single bond with the central carbon atom is called N 2 It is called nitrogen. Similarly, N 1 and N 2 The groups attached to the nitrogen atom are N 1 Groups and N 2 This is called the N group. 2 The -phosphinylformamidine group has the general structure [ka] N 2 -phosphinylformamidine group, N 1 and N 2 Nitrogen atom and N 1 and N 2 The group has the same meaning as described for the formamidine group. 2 -phosphinylformamidine group is N 2The amidine group has the general structure: [ka] In the amidine group, the nitrogen atom participating in the double bond with the central carbon atom is N 1 The nitrogen atom that is involved in a single bond with the central carbon atom is called N 2 It is called nitrogen. Similarly, N 1 and N 2 The groups attached to the nitrogen atom are N 1 Groups and N 2 This is called the N group. 2 The -phosphinyl amidine group has the general structure [ka] N 2 -in the phosphinyl amidine group, N 1 and N 2 Nitrogen atom and N 1 and N 2 The group has the same meaning as described for the amidine group. 2 -phosphinyl amidine group is N 2 It has a phosphinyl group attached to the nitrogen atom. 2 Within the -phosphinyl amidine group, the carbon atom between the two nitrogen atoms is the central carbon atom, and any substituents attached to it are referred to as the central carbon group.

[0036] A guanidine group has the general structure [ka] Within the guanidine core, the nitrogen involved in the double bond to the central carbon atom is N 1 The two nitrogen atoms involved in the single bond with the central carbon atom are called nitrogen atoms. 2 Nitrogen and N 3 It is called nitrogen. Similarly, N 1 , N 2, and N 3 The groups attached to the nitrogen atom are N 1 base, N 2 groups, and N 3 This is called the N group. 2 The -phosphinylguanidine group has the general structure [ka] N 2 Within the -phosphinylguanidine group, the nitrogen participating in the double bond with the central carbon atom of the guanidine core is N 1 The nitrogen atom, which is referred to as nitrogen and participates in the single bond to the central carbon atom of the guanidine core and the bond to the phosphorus atom of the phosphinyl group, is N 2 The remaining nitrogen atoms, referred to as nitrogens and involved in single bonds with the central carbon atom of the guanidine core, are N 3 It is called nitrogen. The guanidine core or N 2 It should be noted that the N-phosphinylguanidine group may be part of a larger group (or compound) where guanidine is not included in the name. For example, the compound 7-dimethylphosphinylimidazo[1,2-a]imidazole can be classified as a compound with an imidazo[1,2-a]imidazole core (or a compound with a phosphinylimidazo[1,2-a]imidazole group), but 7-dimethylphosphinylimidazo[1,2-a]imidazole still has the advantage that it has a guanidine core (or N-phosphinylguanidine group). 2 -phosphinylguanidine group), compounds with a guanidine core (or N 2 -phosphinylguanidine group).

[0037] The term "hydrocarbon," whenever used in this specification and claims, refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of particular groups in the hydrocarbon (e.g., a halogenated hydrocarbon indicates that the presence of one or more halogen atoms replaces an equivalent number of hydrogen atoms in the hydrocarbon).

[0038] For purposes of this application, an "inert functional group" is a group that does not substantially interfere with the processes described herein involving the material having the inert functional group and / or does not complex with the metal compound of the metal complex. The term "does not complex with the metal compound" can include groups that are capable of complexing with the metal compound, but in certain molecules described herein, may not complex with the metal compound due to their position within the ligand. For example, ether groups may complex with the metal compound, but N 2 The ether group located at the para position of the substituted phenylphosphinyl group in N-phosphinyl amidine is such that a single metal compound can be used to complex the para-ether group and N-phosphinyl amidine of the same metal complex molecule. 2 Thus, the inert properties of a particular functional group may not only be related to the functional group's inherent inability to form a complex with a metal compound, but may also be related to the position of the functional group within the metal complex. Non-limiting examples of inert functional groups that do not substantially interfere with the processes described herein may include halo (fluoro, chloro, bromo, and iodo), nitro, hydrocarboxy groups (e.g., alkoxy and / or aroxy, among others), sulfidyl groups, and / or hydrocarbyl groups, among others.

[0039] The term "hydrocarbyl" group is used herein in accordance with the definition specified by IUPAC: a monovalent group (i.e., a group containing only carbon and hydrogen) formed by removing a hydrogen atom from a hydrocarbon. Non-limiting examples of hydrocarbyl groups include ethyl, phenyl, tolyl, propenyl, cyclopentyl, and the like. The term "hydrocarbylene" group is also used herein in accordance with the definition specified by IUPAC: a "hydrocarbylene" group refers to a divalent group formed by removing two hydrogen atoms from a hydrocarbon or substituted hydrocarbon, the free valences of which are not involved in the formation of a double bond. By way of example and comparison, exemplary hydrocarbyl and hydrocarbylene groups include aryl and arylene, alkyl and alkanediyl (or "alkylene"), cycloalkyl and cycloalkanediyl (or "cycloalkylene"), aralkyl and aralkanediyl (or "aralkylene"), and the like, respectively. For example, an "arylene" group is used to refer to a divalent group derived from an arene by removal of hydrogen atoms from two ring carbon atoms, according to the IUPAC definition, which may also be referred to as an "arenediyl" group. Examples of hydrocarbylene groups include, but are not limited to, 1,2-phenylene, 1,3-phenylene, 1,2-propanediyl, 1,3-propanediyl, 1,2-ethanediyl, 1,4-butanediyl, 2,3-butanediyl, and methylene (-CH-).

[0040] The term "heterohydrocarbyl" group is used herein to refer to a monovalent group, which may be straight-chained, branched, or cyclic, formed by removing a single hydrogen atom from a heteroatom of a parent "heterohydrocarbon" molecule, where at least one carbon atom has been replaced with a heteroatom. Thus, "heteroatom" refers to a non-carbon atom such as oxygen, sulfur, nitrogen, phosphorus, silicon, etc. Examples of "heterohydrocarbyl" groups formed by removing a single hydrogen atom from a heteroatom of a heterohydrocarbon molecule include, for example, [1] hydrocarbyloxide groups, e.g., alkoxide (-OR) groups such as tert-butoxide or aryloxide (-OAr) groups such as substituted or unsubstituted phenoxides, formed by removing a hydrogen atom from a hydroxyl (OH) group of a parent alcohol or phenol molecule; [2] hydrocarbylsulfide groups, e.g., alkylthiolate (-SR) or arylthiolate (-SAr) groups formed by removing a hydrogen atom from a hydrogen sulfide (-SH) group of an alkylthiol or arylthiol; [3] hydrocarbylamino groups, e.g., alkylamino (-NHR) or arylamino (-NHAr) groups formed by removing a hydrogen atom from an amino (-NH) group of an alkylamine or arylamine molecule; and [4] trihydrocarbylsilyl groups, such as trialkylsilyl (-SiR) or triarylsilyl (-SiAr) groups.

[0041] A "heteroatom ligand" (which may be abbreviated as "HetLig") is a ligand that includes a heteroatom (non-carbon atom) such as oxygen, sulfur, nitrogen, phosphorus, silicon, etc. Disclosed herein are a variety of heteroatom ligands that can be utilized in the computational and synthetic aspects of the present disclosure.

[0042] "Aliphatic" compounds are a class of acyclic or cyclic saturated or unsaturated carbon compounds, excluding aromatic compounds; for example, aliphatic compounds are non-aromatic organic compounds. An "aliphatic group" is a generalized group formed by removing one or more hydrogen atoms (as needed for the particular group) from a carbon atom of an aliphatic compound. Aliphatic compounds, and therefore aliphatic groups, can contain organic functional group(s) and / or atom(s) other than carbon and hydrogen.

[0043] The term "alkane," whenever used in this specification and claims, refers to a saturated hydrocarbon compound. Other identifiers may be utilized to indicate the presence of a particular group in an alkane (e.g., a halogenated alkane indicates that the presence of one or more halogen atoms replaces an equivalent number of hydrogen atoms in the alkane). The term "alkyl group" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing a hydrogen atom from an alkane. Similarly, an "alkylene group" refers to a group formed by removing two hydrogen atoms from an alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms). An "alkane group" is a general term that refers to a group formed by removing one or more hydrogen atoms (as appropriate for the particular group) from an alkane. "Alkyl groups," "alkylene groups," and "alkane groups" may be acyclic or cyclic and / or straight-chained or branched, unless otherwise specified. Primary, secondary, and tertiary alkyl groups are derived by the removal of hydrogen atoms from primary, secondary, and tertiary carbon atoms of alkanes, respectively. n-Alkyl groups can be derived by the removal of hydrogen atoms from the terminal carbon atoms of straight-chain alkanes. Groups of the form RCH2(R≠H), R2CH(R≠H), and R3C(R≠H) are primary, secondary, and tertiary alkyl groups, respectively, where R itself is an alkyl group.

[0044] The term "carbocyclic" group is used herein to refer to a group whose parent compound is a carbocyclic compound (i.e., a cyclic compound in which all ring members are carbon atoms). A carbocyclic group is formed by removing one or more hydrogen atoms from a carbocyclic compound. For example, a carbocyclic group can be a monovalent group formed by removing a hydrogen atom from a carbocyclic compound. Non-limiting examples of carbocyclic groups include, for example, cyclopentyl, cyclohexyl, phenyl, tolyl, naphthyl, and the like.

[0045] A "cycloalkane" is a saturated cyclic hydrocarbon, with or without side chains, such as cyclobutane. Other identifiers can be used to indicate the presence of specific groups in the cycloalkane (e.g., a halogenated cycloalkane indicates that the presence of one or more halogen atoms replaces an equivalent number of hydrogen atoms in the cycloalkane). Unsaturated cyclic hydrocarbons with one endocyclic double bond or one triple bond are called cycloalkenes and cycloalkynes, respectively. Those with more than one such multiple bond are cycloalkadienes, cycloalkatrienes, etc. Other identifiers can be used to indicate the presence of specific groups in the cycloalkene, cycloalkadienes, cycloalkatrienes, etc.

[0046] A "cycloalkyl" group is a univalent group derived from a cycloalkane by removing a hydrogen atom from a ring carbon atom. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups. For clarity, other examples of cycloalkyl groups include 1-methylcyclopropyl and 2-methylcyclopropyl groups, as illustrated below. [ka] "Cycloalkane group" refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group, at least one of which is a ring carbon) from a cycloalkane.

[0047] The term "alkene," whenever used in this specification and claims, refers to an olefin having at least one carbon-carbon double bond. The term "alkene," unless expressly specified otherwise, includes aliphatic or aromatic, cyclic or acyclic, and / or straight-chain and branched alkenes. The term "alkene," by itself, does not denote the presence or absence of heteroatoms and / or other carbon-carbon double bonds unless expressly indicated. Other identifiers may be used to denote the presence or absence of particular groups within the alkene. Alkenes may also be further specified by the position of the carbon-carbon double bond. Alkenes with more than one such multiple bond are alkadienes, alkatrienes, etc., and may be further specified by the position of the carbon-carbon double bond.

[0048] An "alkenyl group" is a univalent group derived from an alkene by the removal of a hydrogen atom from any carbon atom of the alkene. Thus, an "alkenyl group" is one in which the hydrogen atom is sp 2 Groups that are formally removed from hybridized (olefinic) carbon atoms and hydrogen atoms that are sp 3 This includes groups that are formally removed from any other carbon atom, such as a hybridized carbon atom. For example, unless otherwise specified, 1-propenyl (-CH=CHCH), 2-propenyl [(CH)C=CH], and 3-propenyl (-CHCH=CH) groups are all encompassed by the term "alkenyl group." In this aspect, 3-propenyl (-CHCH=CH) groups are considered alkenyl groups with a terminal C=C double bond, as is 4-butenyl (-CHCHCH=CH). Other identifiers may be used to indicate the presence or absence of particular groups within the alkene group. Alkene groups may also be further specified by the position of the carbon-carbon double bond. Similarly, a "cycloalkenyl" group is a monovalent group derived from a cycloalkene by removal of a hydrogen atom from any carbon atom of the cycloalkene, provided that that carbon atom is not sp 2 Hybridized (olefinic) carbon atoms or sp 3 It does not matter whether the carbon atom is hybridized.

[0049] The term "olefin" is used herein in accordance with the definition set forth by IUPAC: acyclic and cyclic hydrocarbons having one or more carbon-carbon double bonds in addition to the formal double bonds in aromatic compounds. Thus, unless expressly specified otherwise, the term "olefin" includes aliphatic and aromatic, acyclic and cyclic, and / or linear and branched compounds having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. The classification "olefin" encompasses alkenes and cycloalkenes and the corresponding polyenes. Ethylene, propylene, 1-butene, 2-butene, 1-hexene, etc. are non-limiting examples of olefins. The term "alpha olefin," as used herein and in the claims, refers to an olefin having a double bond between the first and second carbon atoms of the longest continuous carbon chain. The term "alpha olefin" includes linear and branched alpha olefins unless expressly specified otherwise. With respect to the olefin oligomerization reactions of this disclosure, the computational and reaction studies are carried out using ethylene, and therefore, unless the context of this disclosure permits or requires otherwise, use of the term "olefin" generally refers to ethylene.

[0050] In accordance with the context of the present disclosure, and unless otherwise specified, the abbreviation "C6" or "C6" may be used to refer to all hydrocarbon compounds having 6 carbon atoms, and the abbreviation "C8" or "C8" may be used to refer to all hydrocarbon compounds having 8 carbon atoms.

[0051] An "aromatic group" refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group, at least one of which is an aromatic ring carbon atom) from an aromatic compound. Thus, as used herein, an "aromatic group" refers to a group derived by removing one or more hydrogen atoms from an aromatic compound, i.e., a compound containing cyclic conjugated hydrocarbons conforming to the Hückel (4n+2) rule and containing (4n+2) pi electrons (where n is an integer from 1 to about 5). Aromatic compounds, and therefore "aromatic groups," can be monocyclic or polycyclic unless otherwise specified. Aromatic compounds include "arenes" (hydrocarbon aromatic compounds) and "heteroarenes," also known as "hetarenes" (heteroaromatic compounds formally derived from arenes by the replacement of one or more methine (-C=) carbon atoms with trivalent or divalent heteroatoms in such a manner as to maintain the continuous pi electron system and some out-of-plane pi electrons characteristic of aromatic systems conforming to the Hückel (4n+2) rule). Arene compounds and heteroarene compounds are mutually exclusive members of the aromatic compound group, but compounds having both arene and heteroarene groups are generally considered heteroarene compounds. Aromatic compounds, arenes, and heteroarenes may be monocyclic or polycyclic unless otherwise specified. Examples of arenes include, but are not limited to, benzene, naphthalene, and toluene, among others. Examples of heteroarenes include, but are not limited to, furan, pyridine, and methylpyridine, among others. As disclosed herein, the term "substituted" may be used to describe an aromatic group in which any non-hydrogen moiety formally replaces a hydrogen atom in the group and is intended to be non-limiting.

[0052] Arenes are aromatic hydrocarbons (e.g., benzene, toluene, or xylene, among others) with or without side chains. An "aryl group" is a group derived from an arene compound by the formal removal of a hydrogen atom from a carbon atom of an aromatic hydrocarbon ring. An example of an "aryl group" is ortho-tolyl (o-tolyl), the structure of which is shown here: [ka] Arenes can contain a single aromatic hydrocarbon ring (e.g., benzene or toluene), fused aromatic rings (e.g., naphthalene or anthracene), or one or more isolated aromatic rings (e.g., biphenyl) or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane) covalently linked through a bond.

[0053] A "heterocyclic compound" is a cyclic compound having at least two different elements as ring atoms. For example, a heterocyclic compound may contain, among others, a ring containing carbon and nitrogen (e.g., tetrahydropyrrole), a ring containing carbon and oxygen (e.g., tetrahydrofuran), or a ring containing carbon and sulfur (e.g., tetrahydrothiophene). Heterocyclic compounds and heterocyclic groups may be either aliphatic or aromatic.

[0054] An "aralkyl group" is an aryl-substituted alkyl group having a free valence at a non-aromatic carbon atom; for example, benzyl and 2-phenylethyl groups are examples of "aralkyl" groups.

[0055] "Halide" has its ordinary meaning; thus, examples of halides include fluoride, chloride, bromide, and iodide.

[0056] The term "cocatalyst" is used generally herein to refer to compounds such as organoaluminum compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, etc., which may constitute a component of a catalyst composition when used with, for example, the chromium-based catalyst compounds of the present disclosure. The term "cocatalyst" is used without regard to the actual function of the compound or any chemical mechanism by which the compound may act.

[0057] The terms "catalyst composition," "catalyst mixture," "catalyst system," etc., do not depend on the actual product or composition resulting from the contact or reaction of the initial components of the claimed catalyst composition / mixture / system, the nature of the catalyst's active sites, or the fate of the cocatalyst, transition metal catalyst compound(s), any olefin monomer used in the catalytic reaction, etc. Thus, the terms "catalyst composition," "catalyst mixture," "catalyst system," etc., encompass the initial starting components of the composition, as well as any product(s) that may result from the contact of these initial starting components, and this includes both heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition," "catalyst mixture," "catalyst system," etc., are used interchangeably throughout this disclosure.

[0058] The term "organoaluminum compound" is used to describe any compound containing an aluminum-carbon bond. Thus, organoaluminum compounds include, but are not limited to, hydrocarbyl aluminum compounds such as trihydrocarbyl-, dihydrocarbyl-, or monohydrocarbyl aluminum compounds; hydrocarbyl aluminum halide compounds; hydrocarbylalumoxane compounds; and aluminate compounds containing an aluminum-organyl bond such as tetrakis(p-tolyl)aluminate. The terms "organoboron" compounds, "organozinc compounds," "organomagnesium compounds," and "organolithium compounds" are used in a similar manner to describe any compound containing a direct metal-carbon bond between the organic group and the stated metal.

[0059] References to gaseous, liquid, and / or solid materials refer to the physical state of the materials at 25° C. and atmospheric pressure.

[0060] Features provided within this disclosure as minimum values ​​may alternatively be defined as "at least" any stated minimum value with respect to the feature disclosed herein, or "greater than or equal to" any stated minimum value. Features provided within this disclosure as maximum values ​​may alternatively be defined as "less than or equal to" with respect to the feature disclosed herein.

[0061] Normal rules of organic nomenclature are used extensively within this disclosure. For example, when referring to a substituted compound or group, reference to a substitution pattern shall be construed to indicate that the indicated group(s) are located at the indicated position, and that all other unrepresented positions are hydrogen. For example, reference to a 4-substituted phenyl group indicates that there is a non-hydrogen substituent at the 4 position, and that there are hydrogens at the 2, 3, 5, and 6 positions. As another example, reference to a 3-substituted naphth-2-yl indicates that there is a non-hydrogen substituent at the 3 position, and that there are hydrogens at the 1, 4, 5, 6, 7, and 8 positions. Reference to a compound or group having substitutions at multiple positions in addition to the indicated position will be referred to using ~, including, or some other alternative expression. For example, reference to a phenyl group containing a substituent at the 4 position refers to the group having a non-hydrogen atom at the 4 position, and hydrogen or any non-hydrogen group at the 2, 3, 5, and 6 positions.

[0062] Described herein are processes for forming oligomeric products. Such processes generally involve contacting ethylene and a catalyst system (or alternatively, contacting ethylene and components of a catalyst system) under oligomerization conditions to form the oligomeric products.

[0063] The term "oligomerization," and its derivatives, refers to a process that produces a mixture of products containing at least 70 weight percent of products containing 2 to 30 ethylene units. Similarly, as used herein, an "oligomer" is a product containing 2 to 30 ethylene units, while an "oligomerization product" or "oligomeric product" includes all products made by the process, including "oligomers" and products that are not "oligomeric" (e.g., products containing more than 30 ethylene units). Furthermore, the terms "oligomer product" and "oligomerization product" may be used interchangeably.

[0064] The term "trimerization" and its derivatives refer to a process that produces a mixture of products containing at least 70 weight percent of products containing three and only three ethylene units. A "trimer" is a product that contains three and only three ethylene units, while a "trimerized product" includes all products made by the trimerization process, including trimers and non-trimeric products (e.g., dimers or tetramers). Generally, a "trimerization" process using ethylene produces an oligomeric product containing at least 70 weight percent hexene(s).

[0065] The term "tetramerization" and its derivatives refer to a process that produces a mixture of products containing at least 70 weight percent of products containing four and only four ethylene units. A "tetramer" is a product that contains four and only four ethylene units, while a "tetramerized product" includes all products made by the tetramerization process, including tetramers and non-tetrameric products (e.g., dimers or trimers). Generally, a "tetramerization" process using ethylene produces an oligomeric product containing at least 70 weight percent octene(s).

[0066] The term "trimerization and tetramerization," and its derivatives, refers to a process that produces a mixture of products containing at least 70 weight percent of products containing three and / or four and only three and / or four ethylene units. "Trimerization and tetramerization products" include all products made by the "trimerization and tetramerization" process, including trimers, tetramers, and non-tetrameric products (e.g., dimers). Generally, the "trimerization and tetramerization" process using ethylene produces oligomeric products containing at least 70 weight percent hexene(s) and / or octene(s).

[0067] Unless otherwise specified, the terms contacted, combined, and "in the presence of" refer to any additional order, sequence, or concentration for contacting or combining two or more components of an oligomerization process. Combining or contacting oligomerization components according to the various methods described herein can occur in one or more contact zones under suitable contacting conditions such as temperature, pressure, contact time, flow rate, etc. The contact zone can be disposed in a vessel (e.g., a storage tank, tote, container, mixing vessel, reactor, etc.), a single conduit (e.g., a tee, inlet, injection port, or header for combining component supply lines into a common line), or any other suitable apparatus for contacting components. The process can be carried out in a batch or continuous process as may be suitable for a given embodiment.

[0068] Use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim.

[0069] This disclosure utilizes Gibbs free energy for many of its calculations, but may also utilize enthalpy and / or Helmholtz energy as approximations to Gibbs free energy.

[0070] The processes described herein can utilize steps, features, compounds, and / or equipment described independently herein. The processes described herein may or may not utilize step identifiers (e.g., 1), 2), etc., a), b), etc., i), ii), etc., or first, second, etc., among others), feature identifiers (e.g., 1), 2), etc., a), b), etc., i), ii), etc., or first, second, etc., among others), and / or compound and / or composition identifiers (e.g., 1), 2), etc., a), b), etc., i), ii), etc., or first, second, etc., among others). However, it should be noted that the processes described herein can have multiple steps, features (e.g., reagent ratios, formation conditions, among other considerations), and / or multiple compounds and / or compositions without the use of descriptors or sometimes with the same general identifier. As a result, it should be noted that the processes described herein may be modified to use any suitable step or feature identifier (e.g., 1), 2), etc., a), b), etc., i), ii), etc., or first, second, etc.), feature identifier (e.g., 1), 2), etc., a), b), etc., i), ii), etc., or first, second, etc.,, and / or compound identifier (e.g., first, second, etc., among others), and that step or feature identifiers may be added and / or modified to indicate different individual steps / features / compounds utilized within the process without detracting from the general disclosure.

[0071] All publications and patents mentioned herein are incorporated by reference for the purpose of describing and disclosing, for example, the constructs and methodologies described in the publications, which may be used in connection with the invention(s) described herein. The publications discussed throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein should be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

[0072] General method description In designing new heteroatom ligand-metal compound complex (e.g., heteroatom ligand-chromium compound complex) catalyst systems capable of producing products with improved activity / productivity, product purity, and selectivity (e.g., increased selectivity to 1-hexene or 1-octene), the design process can involve an iterative process of identifying and adjusting key structural or electronic features of the "trainer" heteroatom ligand-metal compound complex that affect the relative energies of the ground and transition states with respect to activity / productivity, selectivity (1-octene versus 1-hexene production), and product purity (1-hexene versus other C6 products and / or 1-octene versus other C8 products). The design process can also be utilized to improve the selectivity of the trimerization catalytic cycle to 1-hexene (also referred to as trimerization cycle selectivity to 1-hexene), the selectivity of the tetramerization catalytic cycle to 1-octene, and / or the 1-octene efficiency of the fourth ethylene addition. These key structural or electronic features can be used as input variables for the development of a computational design that explores the relative energies of the ground and transition states and, therefore, their relative importance in influencing the overall activity / productivity, product purity, and selectivity of the oligomerization process. Based on this computational design, "target" heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes) can be identified according to the desired tuning of structural or electronic features, and these target complexes can be synthesized and experimentally validated. Based on these results, computational redesign or iteration can be used to identify next-generation target complexes, which can also be experimentally validated and subjected to further testing and redesign.

[0073] Thus, in one aspect, the present disclosure provides a method for designing heteroatom ligand-metal compound complexes for olefin oligomerization, the method comprising: (a) n input variables I 1 , I 2 , …I n (n is an integer), and each input variable is selected from one or more ground state model structures GS A1, …GS Ap (p is an integer), and a plurality of transition state model structures TS associated with the one or more ground state model structures. A1 , T.S. A2 , …TS Am (m is an integer), the one or more ground state model structures GS A1 , …GS Ap and each of the plurality of transition state model structures TS A1 , T.S. A2 , …TS Am are derived from one or more first training heteroatom ligand-metal compound complexes, each complex comprising a first training heteroatom ligand; (b) The ground state model structure GS A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS Am For each of the n input variables I 1 , I 2 , …I n assigning a quantitative value to (c) generating, by at least one processor of the device, the ground state model structure G.S. A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS Am determining the relative energies of each of (d) For each n input variables I 1 , I 2 , …I n The quantitative value of and the ground state model structure GS A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS Am generating a machine learning model based on the correlation of each of the relative energies of (e) Based on the machine learning model, [1] the ground state model structure GS A1 , …GS Apand one of the plurality of transition state model structures TS A1 , T.S. A2 , …TS Am [2] the difference in energy between at least one of the transition state model structures TS [ΔG(TS-GS) or ΔΔG(TS-GS)] A1 , T.S. A2 , …TS Am The n input variables I are associated with the energy difference [ΔG(TS-TS) or ΔΔG(TS-TS)] between any two or more of 1 , I 2 , …I n and identifying one or more of: (f) the one or more n input variables I identified from step (e). 1 , I 2 , …I n and generating first target heteroatom ligand-metal compound complexes for olefin oligomerization, each of the first target heteroatom ligand-metal compound complexes having one or more ground state model structures GS B1 , …GS Bx (x is an integer), or a plurality of transition state model structures TS associated with said one or more ground state model structures. B1 , T.S. B2 , …TS By n output variables O having quantitative values ​​corresponding to any of the structural or electronic properties of 1 , O 2 , …O n is characterized by the one or more ground state model structures GS B1 , …GS Bx and each of the plurality of transition state model structures TS B1 , T.S. B2 , …TS By are derived from the first target heteroatom ligand-metal compound complex, each complex comprising a first target heteroatom ligand; (g) identifying one or more performance parameters associated with an olefin oligomerization reaction and values ​​of the performance parameters for the one or more first training heteroatom ligand-metal compound complexes and the first target heteroatom ligand-metal compound complex; (h) the n output variables O of the first target heteroatom ligand-metal compound complex 1 , O 2 , …O n The quantitative value of is calculated based on n new input variables I derived from one or more second training heteroatom ligand-metal compound complexes containing the second training heteroatom ligand for olefin oligomerization. 1.1 , I 2.1 , …I n.1 repeating steps (a)-(f) one or more times using as an input data set n of n, n = 1, n = 2, n = 3, n = 4, n = 5, n = 6, n = 7, n = 8, n = 9, n = 10, n = 11, n = 12, n = 13, n = 14, n = 15, n = 16, n = 17, n = 18, n = 19, n = 20, n = 21, n = 22, n = 23, n = 24, n = 25, n = 26, n = 27, n = 28, n = 29, n = 30, n = 31, n = 32, n = 33, n = 40, n = 41, n = 42, n = 43, n = 44, n = 45, n = 46, n = 47, n = 48, n = 50, n = 51, n = 52, n = 53, n = 54, n = 55, n = 56, n = 57, n = 58, n = 59, n = 60, n = 61, n = 62, n = 63, n = 64, n = 65, n = 66, n = 67, n = 68, n = 69, n = 70, n = 71, n = 72, n = 73, n = 74, n = 75, n = 76, n = 77, n = 78, n = 79, n = 80, n = 81, n = 82, n = 83, n = 84, n = 85, n = 86, n = 87, n = 88, n = 89, n = 9 1.1 , O 2.1 , …O n.1 and a performance parameter value of one or more second target heteroatom ligand-metal compound complexes; Includes.

[0074] In this embodiment, each of the n input variables I 1 , I 2 , …I n In step (b) of assigning quantitative values ​​to the ground state model structure G.sub.S., these assigned quantitative values ​​may be independently assigned raw values ​​or normalized values. Also in this embodiment, the ground state model structure G.sub.S. A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS AmIn step (c), the determined relative energies may independently be the relative energies of a possible ensemble of conformations of the ground state model structure and the transition state model structure or one specific conformation. This aspect further includes, in step (e), determining n input variables I associated with [1] ΔG(TS-GS) or ΔΔG(TS-GS) or [2] ΔG(TS-TS) or ΔΔG(TS-TS). 1 , I 2 , …I n In identifying one or more of these ΔG or ΔΔG energy differences, these ΔG or ΔΔG energy differences can be based on Boltzmann ensemble ΔG or ΔΔG values.

[0075] For convenience, the above-described methods may be collectively referred to as the "computational" methods of the present disclosure. In a further aspect, the above-described computational methods include: (i) [1] synthesizing a first target heteroatom ligand and / or a second target heteroatom ligand, or [2] synthesizing a first target heteroatom ligand and / or a second target heteroatom ligand, followed by synthesizing a first target heteroatom ligand-metal compound complex or a second target heteroatom ligand-metal compound complex. It may further include:

[0076] In a still further aspect, according to synthesis step (i), the above process comprises (j) performing an olefin oligomerization reaction by [1] contacting a first target heteroatom ligand or a second target heteroatom ligand, a metal compound, an organometallic compound, and an olefin, or [2] contacting a first target heteroatom ligand-metal compound complex or a second target heteroatom ligand-metal compound complex, an organometallic compound, and an olefin. It may further include:

[0077] Regarding input variables, in the computational method disclosed above, at least one input variable I 1 , I 2 , …In is one or more ground state model structures GS presented in a computational manner. A1 , …GS Ap At least one input variable I 1 , I 2 , …I n In addition, several transition state model structures (TS) are presented using computational methods. A1 , T.S. A2 , …TS Am One or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes may also correspond to at least one structural or electronic property of the one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes. A1 , …GS Ap Each of the transition state model structures TS A1 , T.S. A2 , …TS Am For each of the n input variables I 1 , I 2 , …I n The quantitative values ​​assigned to may be based on calculated, measured, or estimated values, or any combination thereof, and these assigned quantitative values ​​may independently be raw values ​​or normalized values.

[0078] According to one aspect, step (e) of the computational method includes generating one or more ground state model structures GS based on a machine learning model. A1 , …GS Ap and multiple transition state model structures TS A1 , T.S. A2 , …TS Am n input variables I associated with the energy difference [ΔG(TS-GS) or ΔΔG(TS-GS)] between at least one of 1 , I 2 , …I n Step (e) of the computational method disclosed above can also include identifying one or more of the transition state model structures TS based on the machine learning model. A1 , T.S. A2 , …TSAm n input variables I associated with the energy difference [ΔΔG(TS-TS)] between any two or more of 1 , I 2 , …I n One or more of the following may also be specified:

[0079] Thus, in one aspect, the method includes selecting n input variables I that provide the largest or most significant energy difference between any of the one or more ground state models and at least one of the plurality of transition state model structures. 1 , I 2 , …I n One or more of the n input variables I identified in step (e) can be identified and selected, which can bring efficiencies to the method and can lead to the design of next-generation compounds to provide improved performance of desired parameters (e.g., activity / productivity, product purity, and / or selectivity) in both synthetic and computational aspects. For example, one or more of the n input variables I identified in step (e) can be selected. 1 , I 2 , …I n One or more of the n input variables I affect ΔG(TS-GS), ΔΔG(TS-GS), or ΔΔG(TS-TS). 1 , I 2 , …I n [1] one or more ground state model structures GS A1 , …GS Ap and multiple transition state model structures TS A1 , T.S. A2 , …TS Am [2] a difference in energy between at least one of the transition state model structures TS [ΔG(TS-GS) or ΔΔG(TS-GS)] A1 , T.S. A2 , …TS Am The energy difference [ΔG(TS-TS) or ΔΔG(TS-TS)] between any two or more of

[0080] Model ground-state and transition-state structures of heteroatom ligand-metal compound complexes Specific heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes) that may be utilized for computational and synthetic purposes in this work, such as one or more first training heteroatom ligand-metal compound complexes, are: [(HetLig)CrX q L r ] 3-q (A) may have a general formula independently selected from: HetLig represents the one or more first training heteroatom ligands; X is an anionic ligand and q is an integer; L is a neutral ligand and r is an integer; Any two or more of the X and L ligands may be linked to form a multidentate ligand.

[0081] In one embodiment, each of the selected n input variables I 1 , I 2 , …I n is one or more ground state model structures GS of formula (A) A1 , …GS Ap or a plurality of transition state model structures TS associated with one or more ground state model structures. A1 , T.S. A2 , …TS Am The structural or electronic properties of any of

[0082] As described herein, specific input variables that may be utilized in the computational methods may include or be selected from structural and electronic features of the heteroatom ligand-metal compound complex (e.g., heteroatom ligand-chromium compound complex) of Formula (A), including various interatomic distances (e.g., distance from chromium to the heteroatom of the heteroatom ligand), bond angles of certain chromium heteroatom ligands, dihedral angles of various chromium heteroatom ligand atoms, atomic charges on the Cr and / or heteroatoms of the heteroatom ligand-chromium compound complex, and / or specific parameters such as distance (Å) from the pocket and volume percent buried. These structural features, electronic features, and parameters are further provided herein.

[0083] In embodiments of the computational methods described herein, the methods use various model structures from which the methods are applied to derive new structures. These structures include: [1] Ground state model structure GS derived from one or more first training heteroatom ligand-metal compound complexes A1 , …GS Ap , [2] Ground-state model structure GS derived from one or more first target heteroatom ligand-metal compound complexes B1 , …GS Bx , [3] Transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes A1 , T.S. A2 , …TS Am , and [4] Transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes A1 , T.S. A2 , …TS Am , It is depicted according to

[0084] Each of these model structures includes a heteroatom ligand, which may be designated according to the particular complex. For example, the heteroatom ligand in each complex may be designated as the first training heteroatom ligand in model structures [1] and [3] listed herein, or as the first target heteroatom ligand in model structures [2] and [4] listed herein.

[0085] In one embodiment, one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes. A1 , …GS Ap has the following model structure: [ka] may be selected from any of where HetLig represents one or more first training heteroatom ligands, and the model ground state structure GS I -I to GS I The superscript "I" in each of -XIII designates the "educational" or "training" model ground state structure.

[0086] In another aspect, a plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes are provided. A1 , T.S. A2 , …TS Am teeth, [ka] and where HetLig represents one or more first training heteroatom ligands, and the model transition state structure TS I -I to TS I The superscript "I" in each of -XV designates the "educational" or "training" model transition state structure.

[0087] A set of similar model ground state and transition state structures can be used as the target heteroatom ligand-metal compound complex. Thus, one or more ground state model structures GS derived from one or more first target heteroatom ligand-metal compound complexes can be used as the model ground state structure GS. B1 , …GS Bx teeth, [ka] and where HetLig represents one or more first target heteroatom ligands, and the model ground state structure GS T -I to GS T The superscript "T" in each of -XIII designates the target model ground state structure.

[0088] In a further aspect, a plurality of transition state model structures TS derived from one or more first target heteroatom ligand-metal compound complexes are provided. A1 , T.S. A2 , …TS Am teeth, [ka] and where HetLig represents one or more first target heteroatom ligands, and the model transition state structure TS T -I to TS T The superscript "T" in each of -XV designates the target model transition state structure.

[0089] Heteroatom Ligands and Heteroatom Ligand-Metal Compound Complexes Generally, the heteroatomic ligand, or the heteroatomic ligand of the heteroatomic ligand-metal compound complex (e.g., heteroatomic ligand-chromium compound complex), can be any heteroatomic ligand that, when utilized in the catalyst system (or catalyst system mixture) described herein for the processes and / or reaction systems described herein, can form oligomeric products in the reaction zone. In certain embodiments, the heteroatomic ligand, or the heteroatomic ligand of the heteroatomic ligand-metal compound complex (e.g., heteroatomic ligand-chromium compound complex), can be a neutral heteroatomic ligand or an anionic heteroatomic ligand, alternatively a neutral heteroatomic ligand, or alternatively an anionic heteroatomic ligand. In certain embodiments, the neutral heteroatomic ligand can include one or more heteroatom complexing moieties, alternatively two heteroatom complexing moieties, or alternatively three heteroatom complexing moieties. In some embodiments, the anionic heteroatom ligand may also contain one or more neutral heteroatom complexing moieties, alternatively two heteroatom complexing moieties, or alternatively three heteroatom complexing moieties. In some embodiments, each neutral heteroatom complexing moiety of the neutral ligand or an anionic ligand containing a neutral heteroatom complexing moiety may independently be an ether group, a sulfide group, an amine group, an imine group, a phosphine group, a phosphinite group, a phosphonite group, or a phosphite group; alternatively, an ether group, a sulfide group, an amine group, an imine group, or a phosphine group; alternatively, an ether group, alternatively, a sulfide group, alternatively, an amine group, alternatively, an imine group, or alternatively, a phosphine group. In some embodiments, the anionic atom of the anionic heteroatom ligand (which forms a covalent or ionic bond with the chromium of the chromium compound) may be an anionic carbon atom, an anionic oxygen atom, or an anionic nitrogen atom; alternatively, an anionic carbon atom, alternatively, an anionic oxygen atom, or alternatively, an anionic nitrogen atom.

[0090] In some embodiments, for example, the heteroatom ligand-metal compound complex can be a heteroatom ligand chromium compound complex, having the general formula [(HetLig)CrX q L r ] 3-q(A), where HetLig represents one or more first training heteroatom ligands, X is an anionic ligand, q is an integer, L is a neutral ligand, and r is an integer, and any two or more of the X and L ligands may be linked to form a multidentate ligand. Thus, with respect to the general and specific structures disclosed herein below, it is contemplated that any two or more of the X and L ligands may form a chelating ligand in which a bridging moiety links the X ligand, the L ligand, or a combination of the X and L ligands.

[0091] In either embodiment, the heteroatom ligand or the heteroatom ligand of the heteroatom-ligand chromium compound complex is N 2 -Phosphinylformamidine, N 2 -phosphinyl amidine, N 2 -phosphinylguanidine, heterocyclic 2-[(phosphinyl)aminyl]imine, or any combination thereof, alternatively N 2 -Phosphinylformamidine, alternatively N 2 -phosphinyl amidine, alternatively N 2 -phosphinylguanidine, or alternatively heterocyclic 2-[(phosphinyl)aminyl]imine. 2 -phosphinylformamidine can have the structure NPF-1, 2 The N-phosphinyl amidine may have the structure NPA-1, 2 The N-phosphinylguanidine can have the structure Gu-1, Gu-2, Gu-3, Gu-4, or Gu-5, and the heterocyclic 2-[(phosphinyl)aminyl]imine can have the structure HCPA-1. 2 -phosphinylguanidine has structure Gu-2, structure Gu-3, or structure Gu-4, alternatively structure Gu-1, alternatively structure Gu-2, alternatively structure Gu-3, alternatively structure Gu-4, or alternatively structure Gu-5. [ka]

[0092] In either embodiment, the heteroatom-ligand chromium compound complex is 2 -Phosphinylformamidine chromium compound complex, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine chromium compound complexes, heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complexes, or any combination thereof, alternatively N 2 -Phosphinylformamidine chromium compound complexes, alternatively N 2 -Phosphinyl amidine chromium compound complexes, alternatively N 2 -phosphinylguanidine chromium compound complexes, alternatively N 2 The compound may comprise, consist essentially of, or be a N-phosphinylguanidine chromium compound complex, or alternatively a heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex. 2 The N-phosphinylformamidine chromium compound complex may have the structure NPFCr-1, 2 The N-phosphinyl amidine chromium compound complex may have the structure NPACr-1, 2 The N-phosphinylguanidine chromium compound complex can have the structure GuCr-1, GuCr-2, GuCr-3, GuCr-4, or GuCr-5, and the heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex can have the structure HCPACr-1. 2 The -phosphinylguanidine chromium compound complex has the structure GuCr-2, the structure GuCr-3, or the structure GuCr-4, alternatively the structure GuCr-r1, alternatively the structure GuCr-2, alternatively the structure GuCr-3, alternatively the structure GuCr-4, or alternatively the structure GuCr-5. [ka]

[0093] N 2 -Phosphinylformamidine, N2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 In the -phosphinylamidine chromium compound complex and the heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex, the nitrogen participating in the double bond with the central carbon atom is N 1 The nitrogen atom that is involved in a single bond with the central carbon atom is called N 2 It is called nitrogen. Similarly, N 2 -phosphinylguanidine and N 2 In the -phosphinylguanidine chromium compound complex, the nitrogen participating in the double bond with the central carbon atom of the guanidine core is N 1 The nitrogen atom, which is referred to as nitrogen and participates in the single bond to the central carbon atom of the guanidine core and the bond to the phosphorus atom of the phosphinyl group, is N 2 The remaining nitrogen atoms, referred to as nitrogens and involved in single bonds with the central carbon atom of the guanidine core, are N 3 It is called nitrogen. 2 -phosphinylguanidine and N 2 It should be noted that the guanidine group of the guanidine in the -phosphinylguanidine chromium complex may be part of a larger group that does not include guanidine in the name. For example, the compound 7-dimethylphosphinylimidazo[1,2-a]imidazole could be classified as a compound with an imidazo[1,2-a]imidazole core (or a compound with a phosphinylimidazo[1,2-a]imidazole group), but 7-dimethylphosphinylimidazo[1,2-a]imidazole would still be classified as a compound with a guanidine core (or a compound with a guanidine group) because it contains the defined general structure of a guanidine compound.

[0094] N 2 -phosphinylformamidine structure and N 2 -R in the structure of phosphinylformamidine chromium compound complexes 1 , R 3 , R 4 , and R 5 base, N 2-phosphinyl amidine structure and N 2 -R in the structure of phosphinyl amidine chromium compound complexes 1 , R 2 , R 3 , R 4 , and R 5 , N 2 -phosphinylguanidine structure and N 2 -R in the structure of phosphinylguanidine chromium compound complexes 1 , R 2a , R 2b , R 3 , R 4 , R 5 , L 12 , L 22 , and L 23 , and L in the heterocyclic 2-[(phosphinyl)aminyl]imine structure and the heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex structure. 12 , T, R 3 , R 4 , and R 5 are independently described herein and are N 2 -Phosphinylformamidine structure, N 2 -phosphinylformamidine chromium compound complex structure, N 2 -phosphinyl amidine structure, N 2 -phosphinyl amidine chromium compound complex structure, N 2 -phosphinylguanidine structure, N 2 The N-phosphinylguanidine chromium compound complex structures, heterocyclic 2-[(phosphinyl)aminyl]imine structures, and heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex structures may be used in any combination, without limitation, to further describe the N-phosphinylguanidine chromium compound complex structures. 2 -phosphinylformamidine chromium compound complex structure, N 2 -phosphinyl amidine chromium compound complex structure, N 2 -X of the structure of phosphinylguanidine chromium compound complexes and the structure of heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complexes p , Q, and q are independently described herein and are N2 -phosphinylformamidine chromium compound complex structure, N 2 -phosphinyl amidine chromium compound complex structure, N 2 The structures of the X-phosphinylguanidine chromium compound complexes and the heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complexes may be used in any combination, without limitation, to further illustrate the structure of the X-phosphinylguanidine chromium compound complexes and the heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complexes. p , Q, and q are independent terms that are used to describe the appropriate N 2 -phosphinylformamidine chromium compound complex structure, N 2 -phosphinyl amidine chromium compound complex structure, N 2 To further illustrate the structure of the 2-[(phosphinyl)aminyl]imine chromium compound complexes and the structure of the heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complexes, the R 1 , R 2 , R 2a , R 2b , R 3 , R 4 , R 5 , L 12 , L 22 , and L 23 It can be combined with.

[0095] In general, R 1 N with group 2 -Phosphinylformamidine, N 2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine, and / or N 2 -R Phosphinylguanidine Chromium Compound Complexes 1 may be an organyl group, alternatively an organyl group consisting of an inert functional group, or alternatively a hydrocarbyl group. 1 Organyl groups are C1-C 20 , C1~C 15 , C1~C 10or a C1-C5 organyl group. In some embodiments, R 1 The organyl group is an inert functional group consisting of C1-C 20 , C1~C 15 , C1~C 10 , or a C1-C5 organyl group. 1 The hydrocarbyl group is C1 to C 20 , C1~C 15 , C1~C 10 , or a C1 to C5 hydrocarbyl group.

[0096] In some embodiments, R 1 N with group 2 -Phosphinylformamidine, N 2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine, and / or N 2 -R Phosphinylguanidine Chromium Compound Complexes 1 may be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group; alternatively, an alkyl group or a substituted alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; alternatively, an aralkyl group or a substituted aralkyl group; alternatively, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; alternatively, an alkyl group, alternatively, a substituted alkyl group, alternatively, a cycloalkyl group, alternatively, a substituted cycloalkyl group, alternatively, an aryl group, alternatively, a substituted aryl group, alternatively, an aralkyl group, or alternatively, a substituted aralkyl group. In any embodiment disclosed herein, R 1 The alkyl group is C1 to C 20 , C1~C 10 or a C1-C5 alkyl group. In any embodiment disclosed herein, R 1 The substituted alkyl group is C1-C 20 , C1~C10 or a C1-C5 substituted alkyl group. In any of the embodiments disclosed herein, R 1 The cycloalkyl group is C4-C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 1 The substituted cycloalkyl group is C4-C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 1 The aryl group is C6-C 20 , C6~C 15 , or C6~C 10 In any embodiment disclosed herein, R 1 The substituted aryl group is C6-C 20 , C6~C 15 , or C6~C 10 In any of the embodiments disclosed herein, R 1 Aralkyl groups are C7-C 20 , C7~C 15 , or C7~C 10 In any embodiment disclosed herein, R 1 The substituted aralkyl group is C7-C 20 , C7~C 15 , or C7~C 10It may be a substituted aralkyl group. Each substituent of the substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), and / or substituted aralkyl group (general or specific) may be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are not substituted R 1 may be used without limitation to further describe the groups.

[0097] In some embodiments, R 1 can be a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl group, or alternatively a methyl, ethyl, n-propyl (1-propyl), iso-propyl (2-propyl), tert-butyl (2-methyl-2-propyl), or neopentyl (2,2-dimethyl-1-propyl) group. 1 The alkyl groups that may be utilized as R may be substituted. Each substituent of a substituted alkyl group (general or specific) may independently be a halogen or a hydrocarboxy group, alternatively a halogen, or alternatively a hydrocarboxy group. Substituent halogens and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens and substituent hydrocarboxy groups are independently disclosed herein. 1 may be used without limitation to further illustrate the substituted alkyl groups that may be utilized as substituted alkyl groups.

[0098] In some embodiments, R 1can be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group, alternatively a cyclopentyl group or a substituted cyclopentyl group, or alternatively a cyclohexyl group or a substituted cyclohexyl group. 1 The substituted cycloalkyl group that may be utilized as R may be a 2-substituted cyclohexyl group, a 2,6-disubstituted cyclohexyl group, a 2-substituted cyclopentyl group, or a 2,5-disubstituted cyclopentyl group, alternatively a 2-substituted cyclohexyl group or a 2,6-disubstituted cyclohexyl group, alternatively a 2-substituted cyclopentyl group or a 2,5-disubstituted cyclopentyl group, alternatively a 2-substituted cyclohexyl group or a 2-substituted cyclopentyl group, or alternatively a 2,6-disubstituted cyclohexyl group or a 2,5-disubstituted cyclopentyl group. 1 One or more substituents of a polysubstituted cycloalkyl group utilized as R can be the same or different; alternatively, all of the substituents of a polysubstituted cycloalkyl group can be the same; alternatively, all of the substituents of a polysubstituted cycloalkyl group can be different. Each substituent of a substituted cycloalkyl group having the specified number of ring carbon atoms can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 1 may be used without limitation to further illustrate the substituted cycloalkyl groups (general or specific) that may be used as substituted cycloalkyl groups.

[0099] In a non-limiting embodiment, R 1may be a cyclohexyl group, a 2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group, or alternatively a cyclopentyl group, a 2-alkylcyclopentyl group, or a 2,5-dialkylcyclopentyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 1 can be used without limitation to further illustrate alkylcyclohexyl groups (general and specific), dialkylcyclohexyl groups (general and specific), alkylcyclopentyl groups (general or specific), and / or dialkylcyclopentyl groups (general and specific). Generally, the alkyl substituents on the dialkylcyclohexyl or dialkylcyclopentyl groups can be the same, or alternatively, the alkyl substituents on the dialkylcyclohexyl or dialkylcyclopentyl groups can be different. In some non-limiting aspects, R 1 can be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group. 1 may be a 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, or 2-tert-butylcyclohexyl group, or alternatively a 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-di-tert-butylcyclohexyl group.

[0100] In some embodiments, R 1 can be a phenyl group, a substituted phenyl group, alternatively a phenyl group, or alternatively a substituted phenyl group. 1The substituted phenyl group that may be utilized as R may be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group, alternatively a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl group, alternatively a 3-substituted phenyl group or a 3,5-disubstituted phenyl group, alternatively a 2-substituted phenyl group or a 4-substituted phenyl group, alternatively a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group, or alternatively a 2,4,6-trisubstituted phenyl group. 1 The one or more substituents of the polysubstituted phenyl group utilized as R can be the same or different; alternatively, all of the substituents of the polysubstituted cycloalkyl group can be the same; alternatively, all of the substituents of the polysubstituted cycloalkyl group are different. Each substituent of the substituted phenyl group (generic or specific) can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (generic and specific), and substituent hydrocarboxy groups (generic and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 1 may be used without limitation to further illustrate the substituted phenyl groups (general or specific) that may be utilized as phenyl groups.

[0101] In a non-limiting embodiment, R 1may be a phenyl group, a 2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively a 2-alkylphenyl group or a 4-alkylphenyl group, alternatively a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group; alternatively a 3-alkylphenyl group or a 3,5-dialkylphenyl group; alternatively a 2-alkylphenyl group or a 2,6-dialkylphenyl group; or alternatively a 2,4,6-trialkylphenyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 1 The term "alkyl-substituted phenyl" can be used without limitation to further describe any alkyl-substituted phenyl group that can be utilized as R. Generally, the alkyl substituents of a dialkylphenyl group (general or specific) or a trialkylphenyl group (general or specific) can be the same, or alternatively, the alkyl substituents of a dialkylphenyl group or a trialkylphenyl group can be different. In some non-limiting embodiments, R 1are independently phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl, or 2,4,6-trimethylphenyl; alternatively phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, or 2-tert-butylphenyl; alternatively phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl, or 2,4,6-trimethylphenyl.

[0102] In some embodiments, R 1 may be a benzyl group or a substituted benzyl group, alternatively a benzyl group, or alternatively a substituted benzyl group. Each substituent of the substituted benzyl group may independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group, alternatively a halogen or a hydrocarbyl group, alternatively a halogen or a hydrocarboxy group, alternatively a hydrocarbyl group or a hydrocarboxy group, alternatively a halogen, alternatively a hydrocarbyl group, or alternatively a hydrocarboxy group. The substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 1 may be used without limitation to further illustrate the substituted benzyl groups (general or specific) that may be used as

[0103] In general, N 2 -phosphinyl amidine and / or N 2 -R Phosphinylamidine Chromium Compound Complexes 2may be an organyl group, alternatively an organyl group consisting of an inert functional group, or alternatively a hydrocarbyl group. 2 Organyl groups are C1-C 20 , C1~C 15 , C1~C 10 or a C1-C5 organyl group. In some embodiments, R 2 The organyl group is an inert functional group consisting of C1-C 20 , C1~C 15 , C1~C 10 , or a C1-C5 organyl group. 2 The hydrocarbyl group is C1 to C 20 , C1~C 15 , C1~C 10 , or a C1 to C5 hydrocarbyl group.

[0104] In some embodiments, N 2 -phosphinyl amidine and / or N 2 -R Phosphinylamidine Chromium Compound Complexes 2 may be an acyl group or a substituted acyl group; an acyl group, or alternatively a substituted acyl group. In some embodiments, the acyl group is a C1-C 20 , C1~C 15 , C1~C 10 or a C1 to C5 acyl group. In some embodiments, the substituted acyl group is a C1 to C 20 , C1~C 15 , C1~C 10 , or a C1-C5 substituted acyl group. 2 -phosphinyl amidine and / or N 2 -R Phosphinylamidine Chromium Compound Complexes 2 may be an alkanoyl group, a substituted alkanoyl group, a benzoyl group, or a substituted benzoyl group; alternatively, an alkanoyl group or a substituted alkanoyl group; alternatively, a benzoyl group or a substituted benzoyl group; alternatively, an alkanoyl group, alternatively, a substituted alkanoyl group, alternatively, a benzoyl group, or alternatively, a substituted benzoyl group. In any embodiment disclosed herein, R 2The alkanoyl group is C1-C 20 , C1~C 10 or a C1-C5 alkanoyl group. In any of the embodiments disclosed herein, R 2 The substituted alkanoyl group is C1-C 20 , C1~C 10 , or C1 to C5 substituted R 2 In any embodiment disclosed herein, R 2 The benzoyl group is C7-C 20 , C7~C 15 , or C7~C 10 In any embodiment disclosed herein, R 2 The substituted benzoyl group is C7-C 20 , C1~C 15 , or C1~C 10 replacement R 2 It may be a benzoyl group. Each substituent of the substituted alkanoyl group (general or specific) and / or the substituted benzoyl group (general or specific) may be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively a halogen or a hydrocarbyl group; alternatively a halogen or a hydrocarboxy group; alternatively a hydrocarbyl group or a hydrocarboxy group; alternatively a halogen, alternatively a hydrocarbyl group, or alternatively a hydrocarboxy group. The substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently disclosed herein. 2 The term "substituted alkanoyl group" can be used without limitation to further illustrate the substituted alkanoyl and / or substituted benzoyl groups that can be used as the substituted alkanoyl group.

[0105] In some embodiments, N 2 -phosphinyl amidine and / or N 2 -R Phosphinylamidine Chromium Compound Complexes 2may be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group; alternatively, an alkyl group or a substituted alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; alternatively, an aralkyl group or a substituted aralkyl group; or alternatively, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. 2 -phosphinyl amidine and / or N 2 -R Phosphinylamidine Chromium Compound Complexes 2 may be an alkyl group, alternatively a substituted alkyl group, alternatively a cycloalkyl group, alternatively a substituted cycloalkyl group, alternatively an aryl group, alternatively a substituted aryl group, alternatively an aralkyl group, or alternatively a substituted aralkyl group. 2 The alkyl group is C1 to C 20 , C1~C 10 or a C1-C5 alkyl group. In any embodiment disclosed herein, R 2 The substituted alkyl group is C1-C 20 , C1~C 10 or a C1-C5 substituted alkyl group. In any of the embodiments disclosed herein, R 2 The cycloalkyl group is C4-C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 2 The substituted cycloalkyl group is C4-C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 2 The aryl group is C6-C 20 , C6~C 15 , or C6~C 10 In any embodiment disclosed herein, R 2 The substituted aryl group is C6-C 20 , C6~C15 , or C6~C 10 In any of the embodiments disclosed herein, R 2 Aralkyl groups are C7-C 20 , C7~C 15 , or C7~C 10 In any embodiment disclosed herein, R 2 The substituted aryl group is C7-C 20 , C7~C 15 , or C7~C 10 It may be a substituted aralkyl group. Each substituent of the substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), and / or substituted aralkyl group (general or specific) may be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 2 can be used without limitation to further explain.

[0106] In some embodiments, R 2 can be a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl group, or alternatively a methyl, ethyl, n-propyl (1-propyl), iso-propyl (2-propyl), tert-butyl (2-methyl-2-propyl), or neopentyl (2,2-dimethyl-1-propyl) group. 2The alkyl groups that may be utilized as R may be substituted. Each substituent of the substituted alkyl group may independently be a halogen or a hydrocarboxy group, alternatively a halogen, or alternatively a hydrocarboxy group. The substituent halogen and the substituent hydrocarboxy groups (general and specific) are disclosed independently herein. These substituent halogen and substituent hydrocarboxy groups are also disclosed in R. 2 may be used without limitation to further illustrate the substituted alkyl groups (general or specific) that may be utilized as substituted alkyl groups.

[0107] In some embodiments, R 2 can be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group, alternatively a cyclopentyl group or a substituted cyclopentyl group, or alternatively a cyclohexyl group or a substituted cyclohexyl group. 2 The substituted cycloalkyl group that may be utilized as R may be a 2-substituted cyclohexyl group, a 2,6-disubstituted cyclohexyl group, a 2-substituted cyclopentyl group, or a 2,5-disubstituted cyclopentyl group, alternatively a 2-substituted cyclohexyl group or a 2,6-disubstituted cyclohexyl group, alternatively a 2-substituted cyclopentyl group or a 2,5-disubstituted cyclopentyl group, alternatively a 2-substituted cyclohexyl group or a 2-substituted cyclopentyl group, or alternatively a 2,6-disubstituted cyclohexyl group or a 2,5-disubstituted cyclopentyl group. 2One or more substituents of a polysubstituted cycloalkyl group utilized as R can be the same or different, alternatively, all of the substituents of a polysubstituted cycloalkyl group can be the same, or alternatively, all of the substituents of a polysubstituted cycloalkyl group can be different. Each substituent of a cycloalkyl group having the specified number of ring carbon atoms can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 2 may be used without limitation to further illustrate the substituted cycloalkyl groups (general or specific) that may be used as substituted cycloalkyl groups.

[0108] In a non-limiting embodiment, R 2 may be a cyclohexyl group, a 2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group, or alternatively a cyclopentyl group, a 2-alkylcyclopentyl group, or a 2,5-dialkylcyclopentyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 2 can be used without limitation to further illustrate alkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups (general or specific), alkylcyclopentyl groups (general or specific), and / or dialkylcyclopentyl groups (general or specific). Generally, the alkyl substituents of disubstituted cyclohexyl or cyclopentyl groups can be the same, or alternatively, the alkyl substituents of dialkylcyclohexyl or cyclopentyl groups can be different. In some non-limiting aspects, R 2can be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group. 2 may be a 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, or 2-tert-butylcyclohexyl group, or alternatively a 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-di-tert-butylcyclohexyl group.

[0109] In some embodiments, R 2 can be a phenyl group, a substituted phenyl group, alternatively a phenyl group, or alternatively a substituted phenyl group. 2 The substituted phenyl group that may be utilized as R may be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group, alternatively a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl group, alternatively a 3-substituted phenyl group or a 3,5-disubstituted phenyl group, alternatively a 2-substituted phenyl group or a 4-substituted phenyl group, alternatively a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group, or alternatively a 2,4,6-trisubstituted phenyl group. 2The one or more substituents of the polysubstituted phenyl group utilized as R can be the same or different; alternatively, all of the substituents of the polysubstituted cycloalkyl group can be the same; alternatively, all of the substituents of the polysubstituted cycloalkyl group can be different. Each substituent of the substituted phenyl group (generic or specific) can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (generic and specific), and substituent hydrocarboxy groups (generic and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 2 may be used without limitation to further illustrate the substituted phenyl groups (general or specific) that may be utilized as phenyl groups.

[0110] In a non-limiting embodiment, R 2 may be a phenyl group, a 2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively a 2-alkylphenyl group or a 4-alkylphenyl group, alternatively a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group; alternatively a 3-alkylphenyl group or a 3,5-dialkylphenyl group; alternatively a 2-alkylphenyl group or a 2,6-dialkylphenyl group; or alternatively a 2,4,6-trialkylphenyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 2The term "alkyl-substituted phenyl" can be used without limitation to further describe any alkyl-substituted phenyl group that can be utilized as R. Generally, the alkyl substituents of a dialkylphenyl group (general or specific) or a trialkylphenyl group (general or specific) can be the same, or alternatively, the alkyl substituents of a dialkylphenyl group or a trialkylphenyl group can be different. In some non-limiting embodiments, R 2 are independently phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl, or 2,4,6-trimethylphenyl; alternatively phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, or 2-tert-butylphenyl; alternatively phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl, or 2,4,6-trimethylphenyl.

[0111] In a non-limiting embodiment, R 2 can be a phenyl group, a 2-alkoxyphenyl group, or a 4-alkoxyphenyl group. 2can be a phenyl group, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, a 2-tert-butoxyphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group, alternatively a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a 2-tert-butoxyphenyl group, or alternatively a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group. 2 can be a phenyl group, a 2-halophenyl group, a 4-halophenyl group, or a 2,6-dihalophenyl group. In general, the halides of the dihalophenyl groups can be the same, or alternatively, the halides of the dihalophenyl groups can be different. In some embodiments, R 2 can be a phenyl group, a 2-fluorophenyl group, a 4-fluorophenyl group, or a 2,6-difluorophenyl group.

[0112] In some embodiments, R 2 may be a benzyl group or a substituted benzyl group, alternatively a benzyl group, or alternatively a substituted benzyl group. Each substituent of the substituted benzyl group may independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group, alternatively a halogen or a hydrocarbyl group, alternatively a halogen or a hydrocarboxy group, alternatively a hydrocarbyl group or a hydrocarboxy group, alternatively a halogen, alternatively a hydrocarbyl group, or alternatively a hydrocarboxy group. The substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 2 The following may be used without limitation to further illustrate the substituted benzyl groups that may be utilized as:

[0113] In a further aspect, R 1 and R 2combines to form N 2 -phosphinyl amidine and / or N 2 R -phosphinyl amidine chromium compound complexes may form rings or ring systems containing the carbon-nitrogen double bond. 1 and R 2 The bond of L 12r and may be an organylene group, alternatively an organylene group consisting of an inert functional group, alternatively a hydrocarbylene group, or alternatively an alkylene group. 12r The organylene group is C3-C 30 , C3~C 20 , C3~C 15 , or C3~C 10 In some embodiments, L, when present, comprises an inert functional group. 12r The organylene group is a C3-C 30 , C3~C 20 , C3~C 15 , or C3~C 10 In other embodiments, when present, L 12r The hydrocarbyl groups are independently C3 to C 30 , C3~C 20 , C3~C 15 , or C3~C 10 In a further aspect, when present, L 12r The alkylene groups are independently C3 to C 30 , C3~C 20 , C3~C 15 , or C3~C 10 In some embodiments, L 12r can be a prop-1,3-ylene group, a but-1,3-ylene group, a 3-methylbut-1,3-ylene group (-CH2CH2C(CH3)2-), a but-1,4-ylene group, or a 1,4-pent-1,4-ylene group.

[0114] Generally, T of the heterocyclic 2-[(phosphinyl)aminyl]imine and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex can be oxygen or sulfur. In some embodiments, T of the heterocyclic 2-[(phosphinyl)aminyl]imine and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex can be oxygen, or alternatively sulfur.

[0115] In general, R 2a and / or R 2b N with group 2 -phosphinylguanidine and / or N 2 -R Phosphinylguanidine Chromium Compound Complexes 2a and / or R 2b may independently be hydrogen or an organyl group, alternatively hydrogen or an organyl group consisting of an inert functional group, alternatively hydrogen or a hydrocarbyl group, alternatively hydrogen, alternatively an organyl group, alternatively an organyl group consisting of an inert functional group, or alternatively a hydrocarbyl group. 2a and / or R 2b The organyl groups are independently C1 to C 20 , C1~C 15 , C1~C 10 or a C1-C5 organyl group. In some embodiments, R 2a and / or R 2b The organyl groups are independently C1-C consisting of inert functional groups. 20 , C1~C 15 , C1~C 10 , or a C1-C5 organyl group. 2a and / or R 2b The hydrocarbyl groups are independently C1 to C 20 , C1~C 15 , C1~C 10 , or a C1 to C5 hydrocarbyl group.

[0116] In some embodiments, R 2a and / or R 2b N with organyl group 2-phosphinylguanidine and / or N 2 -R Phosphinylguanidine Chromium Compound Complexes 2a and R 2b may independently be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group; alternatively, an alkyl group or a substituted alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; alternatively, an aralkyl group or a substituted aralkyl group; alternatively, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; alternatively, an alkyl group, alternatively, a substituted alkyl group, alternatively, a cycloalkyl group, alternatively, a substituted cycloalkyl group, alternatively, an aryl group, alternatively, a substituted aryl group, alternatively, an aralkyl group, or alternatively, a substituted aralkyl group. In any embodiment disclosed herein, R 2a and / or R 2b The alkyl groups are independently C1 to C 20 , C1~C 10 or a C1-C5 alkyl group. In any embodiment disclosed herein, R 2a and / or R 2b The cycloalkyl groups are independently C4 to C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 2a and / or R 2b The substituted cycloalkyl groups are independently C4-C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 2a and / or R 2b The aryl groups are independently C6 to C 20 , C6~C 15 , or C6~C 10 In any embodiment disclosed herein, R 2a and / or R 2b The substituted aryl groups are independently C6-C20 , C6~C 15 , or C6~C 10 It may be a substituted aryl group. Each substituent of the substituted cycloalkyl group (general or specific) and / or the substituted aryl group (general or specific) may be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively a halogen or a hydrocarbyl group; alternatively a halogen or a hydrocarboxy group; alternatively a hydrocarbyl group or a hydrocarboxy group; alternatively a halogen, alternatively a hydrocarbyl group, or alternatively a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently disclosed herein. 2a and / or R 2b can be used without limitation to further explain.

[0117] In some embodiments, N 2 -phosphinylguanidine and / or N 2 -R Phosphinylguanidine Chromium Compound Complexes 1 and R 2a is bonded to the group L 12 wherein L 12 , N 1 Nitrogen atoms and N 3 The nitrogen atoms form a ring or ring system. 2 -phosphinylguanidine and / or N 2 -R Phosphinylguanidine Chromium Compound Complexes 3 and R 2b is bonded to the group L 23 wherein L 23 , N 2 Nitrogen atoms and N 3 The nitrogen atoms form a ring or ring system. 12 Group and / or L 23 N with group 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complex L 12and / or L 23 L may independently be an organylene group, alternatively an organylene group consisting of an inert functional group, or alternatively a hydrocarbylene group. 12 and / or L 23 The organylene groups are independently C2 to C 20 , C2~C 15 , C2~C 10 or a C2-C5 organylene group. 12 and / or L 23 The organylene groups are independently C2-C2 alkyl groups consisting of inert functional groups. 20 , C2~C 15 , C2~C 10 or a C2-C5 organylene group. 12 and / or L 23 The hydrocarbylene groups are independently C2 to C 20 , C2~C 15 , C2~C 10 , or a C2 to C5 hydrocarbylene group.

[0118] In one embodiment, L 12 N 2 -phosphinylguanidine, N 2 -L of phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)aminyl]imine, and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex 12 , and L 23 N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complex L 23 can have any of the structures provided in Table 1. In some embodiments, L 12 and / or L 23 can have Structure 1L, Structure 2L, Structure 3L, Structure 4L, or Structure 5L. In some embodiments, L 12 and / or L 23 may have Structure 2L or Structure 3L, alternatively Structure 4L or Structure 5L. 12 and / or L 23may have Structure 1L, alternatively Structure 2L, alternatively Structure 3L, alternatively Structure 4L, or alternatively Structure 5L. 2 -phosphinylguanidine and N 2 In one embodiment of the -phosphinylguanidine chromium compound complex, L 12 and / or L 23 may have the structure 6L. 12 or L 23 has the structure 6L, the corresponding R 2b or R 2a is N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complexes 3 Note that there is no double bond to the nitrogen atom. [Table 1]

[0119] In the structure of Table 1, L 12 and / or L 23 The unspecified valence of L, if present, 12 and / or L 23 But, N 2 -phosphinylguanidine and N 2 -phosphinylguanidine chromium compound complex. 12 The unspecified valence of L 12 represents the point of attachment to T and the corresponding nitrogen atom of the heterocyclic 2-[(phosphinyl)aminyl]imine and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex. Generally, m can be an integer ranging from 2 to 5. In further embodiments, m can be 2 or 3, or alternatively, m can be 2, or alternatively, m can be 3. R of a linking group having Structure 1L L1 and R L2 , R of a linking group having Structure 2L L3 , R L4 , R L5 , and RL6 , R of the linking group having Structure 3L L3 , R L4 , R L5 , R L6 , R L7 , and R L8 , R of the linking group having Structure 4L L11 and R L12 , R of the linking group having Structure 5L L23 , R L24 , R L25 , and R L26 , R of the linking group having Structure 6L L27 , R L28 , and R L29 may independently be hydrogen or a non-hydrogen substituent, or alternatively hydrogen. The non-hydrogen substituents (general and specific) are independently disclosed herein and may be utilized without limitation to further describe linking groups having Structure 1L, Structure 2L, Structure 3L, Structure 4L, Structure 5L, and / or Structure 6L. In some embodiments, L 12 and / or L 23 can independently be an eth-1,2-ylene group (-CHCH-), an ethene-1,2-ylene group (-CH=CH-), a prop-1,3-ylene group (-CHCHCH-), a 1-methylethene-1,2-ylene group (-C(CH)=CH-), a but-1,3-ylene group (-CHCHCH(CH)-), a 3-methylbut-1,3-ylene group (-CHCHC(CH)-), or a phen-1,2-ylene group. 12 and / or L 23is an eth-1,2-ylene group (-CH2CH2-), a prop-1,3-ylene group (-CH2CH2CH2-), a 1-methylethen-1,2-ylene group (-C(CH3)=CH-), a but-1,3-ylene group (-CH2CH2CH(CH3)-), or a 3-methylbut-1,3-ylene group (-CH2CH2C(CH3)2-), alternatively an eth-1,2-ylene group (-CH2CH 2-), an ethene-1,2-ylene group (-CH=CH-), a prop-1,3-ylene group (-CHCHCH-), or a phen-1,2-ylene group, alternatively an eth-1,2-ylene group (-CHCH-) or a prop-1,3-ylene group (-CHCHCH-), alternatively an ethene-1,2-ylene group (-CH=CH-) or a phen-1,2-ylene group.

[0120] In one embodiment, L 12 is N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complexes 1 It may contain at least one substituent located on a carbon atom attached to the nitrogen atom, or alternatively, N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complexes 1 It may contain only one substituent located on the carbon atom attached to the nitrogen atom, or alternatively, N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complexes 1 In another embodiment, L may have the structure, which may include two substituents located on the carbon atom attached to the nitrogen atom. 12 is N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complexes 1 It may consist of one substituent located on the carbon atom attached to the nitrogen atom, or alternatively, N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complexes1 It may have a structure which may consist of two substituents located on the carbon atom attached to the nitrogen atom.

[0121] In some embodiments, N 2 -phosphinylguanidine and / or N 2 -R Phosphinylguanidine Chromium Compound Complexes 2a and R 2b is bonded to the group L 22 wherein R 2a , R 2b , and N 3 Nitrogen (or L 22 and N 3 nitrogen) form a ring or ring system. 22 N with group 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complex L 22 L may be an organylene group, alternatively an organylene group consisting of an inert functional group, or alternatively a hydrocarbylene group. 22 The organylene group is C3-C 20 , C3~C 15 , or C3~C 10 L consisting of an inert functional group can be an organylene group. 22 The organylene group is a C3-C 20 , C3~C 15 , or C3~C 10 It may be an organylene group. 22 The hydrocarbylene group is C4 to C 20 , C4~C 15 , or C4~C 10 It may be a hydrocarbylene group.

[0122] In one embodiment, L 22 can have any of the structures provided in Table 2. In some embodiments, L 22 can have Structure 11L, Structure 12L, Structure 13L, Structure 14L, Structure 15L, or Structure 16L. 22may have structure 11L, alternatively structure 12L, alternatively structure 13L, alternatively structure 14L, or alternatively structure 15L. [Table 2]

[0123] Within the structures in Table 2, unspecified valences, when present, are N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complex L 22 But, N 2 -phosphinylguanidine and / or N 2 -Phosphinylguanidine chromium compound complexes 3 represents the point of attachment to the nitrogen atom. Generally, n can be an integer ranging from 4 to 7. In further embodiments, n can be 4 or 5, or alternatively, n can be 4, or alternatively, n can be 5. R of a linking group having structure 11L L31 and R L32 , R of the linking group having structure 12L L41 , R L42 , R L43 , R L44 , R L45 , R L46 , R L47 , and R L48 , R of the linking group having structure 13L L41 , R L42 , R L43 , R L44 , R L45 , R L46 , R L47 , R L48 , R L49 , and R L50 , R of the linking group having structure 14L L41 , R L42 , R L43 , R L44 , R L45 , R L46 , R L47 , and R L48 and R of the linking group having structure 15L. L41 , R L42 , R L43 , RL44 , R L45 , R L46 , R L47 , and R L48 may independently be hydrogen or a non-hydrogen substituent, alternatively hydrogen. The non-hydrogen substituents are independently disclosed herein and may be utilized without limitation to further describe linking groups having Structure 11L, Structure 12L, Structure 13L, Structure 14L, and / or Structure 15L. In some embodiments, L 22 may be a but-1,4-ylene group, a pent-1,4-ylene group, a pent-1,5-ylene group, a hex-2,5-ylene group, a hex-1,5-ylene group, a hept-2,5-ylene group, a buta-1,3-diene-1,4-ylene group, or a bis(eth-2-yl) ether group, or alternatively a but-1,4-ylene group, a pent-1,5-ylene group, or a bis(eth-2-yl) ether group.

[0124] In general, R 3 N with group 2 -Phosphinylformamidine, N 2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine, N 2 -R of phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)aminyl]imine, and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex 3 may be hydrogen or an organyl group, hydrogen or an organyl group consisting of an inert functional group, alternatively hydrogen or a hydrocarbyl group, alternatively hydrogen, alternatively an organyl group, alternatively an organyl group consisting of an inert functional group, or alternatively a hydrocarbyl group. 3 Organyl groups are C1-C 20 , C1~C 15 , C1~C 10 or a C1-C5 organyl group. In some embodiments, R 3 The organyl group is an inert functional group consisting of C1-C20 , C1~C 15 , C1~C 10 , or a C1-C5 organyl group. 3 The hydrocarbyl group is C1 to C 20 , C1~C 15 , C1~C 10 or a C1-C5 hydrocarbyl group. 3 N with group 2 -Phosphinylformamidine, N 2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine, N 2 -R of phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)aminyl]imine, and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex 3 is C1~C 30 , C1~C 20 , C1~C 15 , C1~C 10 or a C1-C5 alkyl group. 2 -Phosphinylformamidine, N 2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine, N 2 -R of phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)aminyl]imine, and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex 3 is a phenyl group or a C6-C 20 Substituted phenyl group, alternatively phenyl group or C6-C 15 Substituted phenyl group, or alternatively phenyl group or C6-C 10 It may be a substituted phenyl group. Substituents (general and specific) are provided herein, and these substituents are R 3Substituted phenyl groups, non-hydrogen R 3 N with group 2 -Phosphinylformamidine, N 2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine, and / or N 2 -phosphinylguanidine chromium compound complexes can be used to further illustrate the

[0125] In general, N 2 -Phosphinylformamidine, N 2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine, N 2 -R of phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)aminyl]imine, and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex 4 and / or R 5 may independently be an organyl group, alternatively an organyl group consisting of an inert functional group, or alternatively a hydrocarbyl group. 4 and / or R 5 Organyl groups are C1-C 20 , C1~C 15 , C1~C 10 or a C1-C5 organyl group. In some embodiments, R 4 and / or R 5 The organyl group is an inert functional group consisting of C1-C 20 , C1~C 15 , C1~C 10 , or a C1-C5 organyl group. 4 and / or R 5 The hydrocarbyl group is C1 to C 20 , C1~C 15 , C1~C10 , or a C1-C5 hydrocarbyl group. 2 -Phosphinylformamidine, N 2 -Phosphinylformamidine chromium compound complex, N 2 -phosphinyl amidine, N 2 -Phosphinyl amidine chromium compound complex, N 2 -phosphinylguanidine, N 2 -R of phosphinylguanidine chromium compound complex, heterocyclic 2-[(phosphinyl)aminyl]imine, and / or heterocyclic 2-[(phosphinyl)aminyl]imine chromium compound complex 4 and / or R 5 may independently be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group; alternatively, an alkyl group or a substituted alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; alternatively, an aralkyl group or a substituted aralkyl group; alternatively, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; alternatively, an alkyl group, alternatively, a substituted alkyl group, alternatively, a cycloalkyl group, alternatively a substituted cycloalkyl group, alternatively, an aryl group, alternatively, a substituted aryl group, alternatively, an aralkyl group, or alternatively, a substituted aralkyl group.

[0126] In any of the embodiments disclosed herein, R 4 and / or R 5 The alkyl groups are independently C1 to C 20 , C1~C 10 or a C1-C5 alkyl group. In any embodiment disclosed herein, R 4 and / or R 5 The substituted alkyl groups are independently C1-C 20 , C1~C 10 or a C1-C5 substituted alkyl group. In any of the embodiments disclosed herein, R 4 and / or R 5 The cycloalkyl groups are independently C4 to C20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 4 and / or R 5 The substituted cycloalkyl groups are independently C4-C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 4 and / or R 5 The aryl groups are independently C6 to C 20 , C6~C 15 , or C6~C 10 In any embodiment disclosed herein, R 4 and / or R 5 The substituted aryl groups are independently C6-C 20 , C6~C 15 , or C6~C 10 In any of the embodiments disclosed herein, R 4 and / or R 5 The aralkyl groups are independently C7-C 20 , C7~C 15 , or C7~C 10 In any embodiment disclosed herein, R 4 and / or R 5 The substituted aryl groups are independently C7-C 20 , C7~C 15 , or C7~C 10It may be a substituted aralkyl group. Each substituent of the substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), and / or substituted aralkyl group (general or specific) may be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 4 and / or R 5 can be used without limitation to further explain.

[0127] In some embodiments, R 4 and R 5 can be independently a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl group, or alternatively a methyl, ethyl, n-propyl (1-propyl), iso-propyl (2-propyl), 2-methyl-1-propyl, tert-butyl (2-methyl-2-propyl), or neopentyl (2,2-dimethyl-1-propyl) group. 4 and / or R 5 The alkyl groups that may be utilized as R may be substituted. Each substituent of the substituted alkyl group may independently be a halogen or a hydrocarboxy group, alternatively a halogen, or alternatively a hydrocarboxy group. Substituent halogen and substituent hydrocarboxy (general and specific) groups are independently disclosed herein. These substituent halogen and substituent hydrocarboxy groups are independently disclosed herein. 4 and / or R 5 may be used without limitation to further illustrate the substituted alkyl groups that may be utilized as substituted alkyl groups.

[0128] In some embodiments, R 4 and R 5 can independently be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group, alternatively a cyclopentyl group or a substituted cyclopentyl group, or alternatively a cyclohexyl group or a substituted cyclohexyl group. 4 and / or R 5 The substituted cycloalkyl groups that may be utilized for may be 2-substituted cyclohexyl, 2,6-disubstituted cyclohexyl, 2-substituted cyclopentyl, or 2,5-disubstituted cyclopentyl, alternatively 2-substituted cyclohexyl or 2,6-disubstituted cyclohexyl, alternatively 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl, alternatively 2-substituted cyclohexyl or 2-substituted cyclopentyl, or alternatively 2,6-disubstituted cyclohexyl or 2,5-disubstituted cyclopentyl. In embodiments where a substituted cycloalkyl group (general or specific) has more than one substituent, the substituents may be the same or different, alternatively the same, or alternatively different. Each substituent of a cycloalkyl group (general or specific) having a specified number of ring carbon atoms can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively a halogen or a hydrocarbyl group; alternatively a halogen or a hydrocarboxy group; alternatively a hydrocarbyl group or a hydrocarboxy group; alternatively a halogen, alternatively a hydrocarbyl group, or alternatively a hydrocarboxy group. The substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 4 and / or R 5 may be used without limitation to further illustrate the substituted cycloalkyl groups (general or specific) that may be used as substituted cycloalkyl groups.

[0129] In a non-limiting embodiment, R 4 and R 5may independently be a cyclohexyl group, a 2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group, or alternatively a cyclopentyl group, a 2-alkylcyclopentyl group, or a 2,5-dialkylcyclopentyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 4 and / or R 5 can be used without limitation to further illustrate alkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups (general or specific), alkylcyclopentyl groups (general or specific), and / or dialkylcyclopentyl groups (general or specific). Generally, the alkyl substituents of disubstituted cyclohexyl or cyclopentyl groups can be the same, or alternatively, the alkyl substituents of dialkylcyclohexyl or cyclopentyl groups can be different. In some non-limiting aspects, R 4 and R 5 can independently be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group. 4 and R 5 may independently be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, or a 2-tert-butylcyclohexyl group, or alternatively a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group.

[0130] In some embodiments, R 4 and R 5 may independently be a phenyl group, a substituted phenyl group, alternatively a phenyl group, or alternatively a substituted phenyl group. 4 and / or R 5The substituted phenyl group that may be utilized for R may be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group, alternatively a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl group, alternatively a 3-substituted phenyl group or a 3,5-disubstituted phenyl group, alternatively a 2-substituted phenyl group or a 4-substituted phenyl group, alternatively a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group, or alternatively a 2,4,6-trisubstituted phenyl group. 4 and / or R 5 The one or more substituents of the polysubstituted phenyl group utilized as R can be the same or different; alternatively, all of the substituents of the polysubstituted cycloalkyl group can be the same; alternatively, all of the substituents of the polysubstituted cycloalkyl group are different. Each substituent of the substituted phenyl group (generic or specific) can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (generic and specific), and substituent hydrocarboxy groups (generic and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 4 and / or R 5 may be used without limitation to further illustrate the substituted phenyl groups (general or specific) that may be utilized as phenyl groups.

[0131] In a non-limiting embodiment, R 4 and R 5may independently be a phenyl group, a 2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively a 2-alkylphenyl group or a 4-alkylphenyl group, alternatively a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group; alternatively a 3-alkylphenyl group or a 3,5-dialkylphenyl group; alternatively a 2-alkylphenyl group or a 2,6-dialkylphenyl group; or alternatively a 2,4,6-trialkylphenyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 4 and / or R 5 The term "alkyl-substituted phenyl" can be used without limitation to further describe any alkyl-substituted phenyl group that can be utilized as R. Generally, the alkyl substituents of a dialkylphenyl group (general or specific) or a trialkylphenyl group (general or specific) can be the same, or alternatively, the alkyl substituents of a dialkylphenyl group (general or specific) or a trialkylphenyl group (general or specific) can be different. In some non-limiting embodiments, R 4 and R 5are independently phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl, or 2,4,6-trimethylphenyl; alternatively phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, or 2-tert-butylphenyl; alternatively phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl, or 2,4,6-trimethylphenyl.

[0132] In a non-limiting embodiment, R 4 and R 5 can be a phenyl group, a 2-alkoxyphenyl group, or a 4-alkoxyphenyl group. 4 and / or R 5 can be a phenyl group, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, a 2-tert-butoxyphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group, alternatively a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a 2-tert-butoxyphenyl group, or alternatively a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group. 4 and R 5can independently be a phenyl group, a 2-halophenyl group, a 4-halophenyl group, or a 2,6-dihalophenyl group. In general, the halides of the dihalophenyl groups can be the same, or alternatively, the halides of the dihalophenyl groups can be different. In some embodiments, R 4 and R 5 can independently be a phenyl group, a 2-fluorophenyl group, a 4-fluorophenyl group, or a 2,6-difluorophenyl group.

[0133] In some embodiments, R 4 and R 5 may independently be a benzyl group or a substituted benzyl group, alternatively a benzyl group, or alternatively a substituted benzyl group. Each substituent of the substituted benzyl group may independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group, alternatively a halogen or a hydrocarbyl group, alternatively a halogen or a hydrocarboxy group, alternatively a hydrocarbyl group or a hydrocarboxy group, alternatively a halogen, alternatively a hydrocarbyl group, or alternatively a hydrocarboxy group. The substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 4 and / or R 5 The following may be used without limitation to further illustrate the substituted benzyl groups that may be utilized as the substituted benzyl groups:

[0134] In a further aspect, R 4 and R 5 may be linked to form a ring or ring system containing a phosphorus atom. 4 and R 5 The bond of L 45 and may be an organylene group, alternatively an organylene group consisting of an inert functional group, alternatively a hydrocarbylene group, or alternatively an alkylene group. 45 The organylene group is C4-C 30 , C4~C 20 , C4~C15 , or C4~C 10 In some embodiments, L, when present, comprises an inert functional group. 45 The organylene group is a C4-C 30 , C4~C 20 , C4~C 15 , or C4~C 10 In some embodiments, when present, L 45 The hydrocarbyl groups are independently C4 to C 30 , C4~C 20 , C4~C 15 , or C4~C 10 In a further aspect, when present, L 45 The alkylene groups are independently C4 to C 30 , C4~C 20 , C4~C 15 , or C4~C 10 In some embodiments, L 45 may be a but-1,4-ylene group, a 1,4-diphenylbut-1,4-ylene group, a 1,4-di(2-methylphenyl)but-1,4-ylene group, a 1,4-di(4-methylphenyl)but-1,4-ylene group, a 1,4-di(4-t-butylphenyl)but-1,4-ylene group, a 1,4-di(3,5-dimethylphenyl)but-1,4-ylene group, a pent-1,4-ylene group, a 1-phenylpent-1,4-ylene group, a 4-phenylpent-1,4-ylene group, a hex-2,5-ylene group, a 2,2′-biphenylene group, a 2,2′-(methanediyl)diphenylene group, or a 2,2′-(1,2-ethanediyl)diphenylene group.

[0135] In some embodiments, the heteroatom ligand or heteroatom ligand of the heteroatom-ligand chromium compound complex has the formula (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n while the heteroatom-ligand chromium compound complexes may have the formula: [ka] may have:

[0136] In some embodiments, the heteroatom ligand or the heteroatom ligand of the heteroatom-ligand chromium compound complex has the formula (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n When the heteroatom ligand has the formula (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n In the case where the compound may have two groups that can be described by 1s The groups are linked so that the heteroatom ligand and the heteroatom ligand chromium compound complex respectively have the formula: [ka] may have:

[0137] Formula (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n or two linked (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n In the heteroatom ligand having a group or the heteroatom ligand of the heteroatom ligand chromium compound complex, each X 1s and each X 2s may be independently selected from the group consisting of N, P, O, and S, and each L 1s are the corresponding X 1s and X 2sand each m and each n can independently be 1 or 2; and each R 1s and each R 2s may independently be hydrogen, an organyl group (or alternatively an organyl group consisting of inert functional groups, or alternatively a hydrocarbyl group), or a heterohydrocarbyl group, where two or more R 1s and / or two R's 2s If there is, then each R 1s may be the same or different (alternatively the same or alternatively different), and / or each R 2s can be the same or different (alternatively the same or alternatively different). 1s , X 1s , X 2s , R 1s , R 2s , m, and n are L 1s , X 1s , X 2s , R 1s , R 2s L is an optional heteroatomic ligand having m, m, and / or n or an independent component of any heteroatomic ligand of a heteroatomic ligand chromium compound complex, as independently described herein. 1s , X 1s , X 2s , R 1s , R 2s These independent descriptions of , m, and n are 1s , X 1s , X 2s , R 1s , R 2s Any heteroatomic ligand having m, m, and / or n or any heteroatomic ligand of a heteroatomic ligand chromium compound complex may be utilized without limitation and in any combination. p are independent elements of the heteroatom-ligand chromium compound complexes and are described herein independently and without limitation to further describe the heteroatom-ligand chromium compound complexes contemplated herein, and the heteroatom-ligand L 1s , X 1s , X 2s , R 1s , R2s , m, and n may be used in any combination.

[0138] In some embodiments, X 1s and / or X 2s Each X of any heteroatom ligand or any heteroatom ligand of any heteroatom ligand chromium compound complex described herein has 1s and each X 2s may be independently selected from N, P, O, and S, or alternatively may be independently selected from N and P, or alternatively may be independently selected from O and S. In some embodiments, each X 1s and each X 2s may be N, alternatively P, alternatively O, or alternatively S. Each m and each n of any heteroatomic ligand described herein or any heteroatomic ligand of any heteroatomic ligand chromium compound complex having m and / or n may be independently selected from 1 or 2, or alternatively may be 1, or alternatively may be 2. In certain embodiments, each X 1s and / or X 2s is O or S, alternatively O, or alternatively S, then each m and / or each n can be 1. In certain other embodiments, each X 1s and / or X 2s When is N or P, alternatively N, or alternatively P, each m and / or each n may be 2.

[0139] In a non-limiting embodiment, the heteroatom ligand has the formula R 1s S(L 1s )SR 2s , (R 1s )2P(L 1s )P(R 2s )2, or (R 1s )2N(L 1s )N(R 2s )2, alternatively R 1s S(L 1s )SR 2s , as an alternative (R 1s )2P(L 1s )P(R 2s)2, or alternatively (R 1s )2N(L 1s )N(R 2s )2, while heteroatom-ligand chromium compound complexes may have the formula [ka] It may have any one of the following:

[0140] In a non-limiting embodiment in which the heteroatomic ligand or heteroatomic ligand of the heteroatomic ligand chromium compound complex has two linked heteroatomic groups, the heteroatomic ligand is [ka] while the heteroatom-ligand chromium compound complexes may have a formula selected from one or more of the formula [ka] It may have any one of the following:

[0141] In some embodiments, each L of any heteroatom ligand or any heteroatom ligand of a heteroatom-ligand chromium compound complex described herein 1s are independently the groups X 1s and X 2s (and more than one L 1s If present, the heteroatom ligand or other L in the case of a heteroatom ligand of a heteroatom-ligand chromium compound complex 1s In some embodiments, each L 1sare independently an organylene group, an amine-diyl group, or a phosphine-diyl group; alternatively, an organylene group, an amine-diyl group, or a phosphine-diyl group consisting of an inert functional group; alternatively, a hydrocarbylene group, an amine-diyl group, or a phosphine-diyl group; alternatively, an amine-diyl group or a phosphine-diyl group; alternatively, an organylene group, alternatively, an organylene group consisting of an inert functional group, alternatively, a hydrocarbylene group, alternatively, an amine-diyl group, or alternatively, a phosphine-diyl group. 1s When groups are present, each L 1s may independently be an organic, amine, or phosphine group, alternatively an organic group consisting of an inert functional group, an amine, or a phosphine group, alternatively a hydrocarbon group, an amine, or a phosphine group, alternatively an amine or a phosphine group, alternatively an organic group, alternatively an organic group consisting of an inert functional group, alternatively a hydrocarbon group, alternatively an amine, or alternatively a phosphine group. 1s The organylene group or organic group is C1-C 20 , C1~C 15 , C1~C 10 or a C1-C5 organylene or organic group. In some embodiments, L is an inert functional group. 1s The organylene group is a C1-C 20 , C1~C 15 , C1~C 10 or a C1-C5 organylene or organic group. 1s The hydrocarbylene group is C1 to C 20 , C1~C 15 , C1~C 10 or a C1-C5 hydrocarbylene or hydrocarbon group. In some embodiments, the amine-di-yl or amine group is a C1-C 30 , C1~C 20 , C1~C 15 , or C1~C 10In some embodiments, the phosphine-di-yl or phosphine group is a C1-C 30 , C1~C 20 , C1~C 15 , or C1~C 10 It may be a phosphine-di-yl or phosphine group.

[0142] In one embodiment, each L 1s The organylene or organic group has the formula -(L 3s )NR 5s (L 4s )-or-(L 3s )PR 5s (L 4s )-, alternatively -(L 3s )NR 5s (L 4s )-, or alternatively -(L 3s )PR 5s (L 4s In some embodiments, each amine-di-yl group can have the formula —N(R 5s In some embodiments, each phosphine-di-yl group can have the formula -P(R 5s )-. These L 1s In the formula of the group, the dashed line represents the X of the heteroatom ligand of the heteroatom ligand or heteroatom ligand of the heteroatom ligand chromium compound complex described herein. 1s and X 2s represents the unspecified valence to which the heteroatom ligand or heteroatom ligand of a heteroatom-ligand chromium compound complex has more than one L 1s When groups are present, each L 1s Group R 5s L 2sIn some non-limiting embodiments, the heteroatom ligands may have the structure PNP1, the structure PNP2, the structure NRNRN, the structure PRPRP, the structure SRNRS, the structure PRNRP, and the structure NRPRN, alternatively the structure PNP1 or the structure PNP2, alternatively the structure PRPRP, the structure SRNRS, or the structure PRNRP, alternatively the structure PNP1, alternatively the structure PNP2, alternatively the structure NRNRN, alternatively the structure PRPRP, alternatively the structure SRNRS, alternatively the structure PRNRP, or alternatively the structure NRPRN. In some non-limiting embodiments, the heteroatom ligands (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n Heteroatom ligand chromium compound complexes having the structure may have the structure PNPCr-1, the structure PNPCr-2, the structure NRNRNCr-1, the structure PRPRPC-1r, the structure SRNRSCr-1, the structure PRNRPC-1r, and the structure NRPRNCr-1, alternatively the structure PNPCr-1 or the structure PNPCr-2, alternatively the structure PRPRPCr-1, the structure SRNRSCr-1, or the structure PRNRPC-1r, alternatively the structure PNPCr-1, alternatively the structure PNPCr-2, alternatively the structure NRNRNC-1r, alternatively the structure PRPRPCr-1, alternatively the structure SRNRSCr-1, alternatively the structure PRNRPCr-1, or alternatively the structure NRPRNC-1r. [ka]

[0143] R 5s , L 2s , L 3s , L 4s , R 11s , R 12s , R 13s , and R 14sare each an independent element of the heteroatomic ligand having the structure PNP-1, the structure PNP-2, the structure NRNRN-1, the structure PRPRP-1, the structure SRNRS-1, the structure PRNRP-1, or the structure NRPRN-1, and / or the heteroatomic ligand of the heteroatomic ligand chromium compound complex having the structure PNPCr-1, the structure PNPCr-2, the structure NRNRNCr-1, the structure PRPRPCr-1, the structure SRNRSCr-1, the structure PRNRPCr-1, and the structure NRPRNCr-1, in which they are present, and are independently described herein. 5s , L 2s , L 3s , L 4s , R 11s , R 12s , R 13s , and R 14s The independent descriptions of X and p may be utilized, without limitation, and in any combination, to further describe the structure of the heteroatomic ligand and / or the structure of the heteroatomic ligand chromium compound complex in which they are present. Similarly, X and p are independent elements of the heteroatomic ligand chromium compound complexes having Structure PNPCr-1, Structure PNPCr-2, Structure NRNRNCr-1, Structure PRPRPCr-1, Structure SRNRSCr-1, Structure PRNRPCr-1, and Structure NRPRNCr-1, and are independently described herein. The independent descriptions of X and p may be utilized, without limitation, and in any combination, to further describe any heteroatomic ligand chromium compound complexes having Structure PNPCr-1, Structure PNPCr-2, Structure NRNRNCr-1, Structure PRPRPCr-1, Structure SRNRSCr-1, Structure PRNRPCr-1, and / or Structure NRPRNCr-1, and are independently described herein. 5s , L 2s , L 3s , L 4s , R 11s , R 12s , R 13s , and R 14s may be used in any combination with

[0144] In general, R 1s , R 2s , R 11s , R 12s , R13s , and / or R 14s The structure of any heteroatom ligand depicted herein having a group and / or the R of any heteroatom ligand chromium compound complex depicted herein 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may independently be an organyl group, alternatively an organyl group consisting of an inert functional group, or alternatively a hydrocarbyl group. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The organyl groups that can be used are independently C1 to C 20 , C1~C 15 , C1~C 10 , or a C1-C5 organyl group. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The organyl groups consisting of inert functional groups that can be used as 20 , C1~C 15 , C1~C 10 or an organyl group consisting of a C1-C5 inert functional group. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The hydrocarbyl groups that may be utilized are independently C1 to C 20 , C1~C 15 , C1~C 10 , or a C1 to C5 hydrocarbyl group.

[0145] In some embodiments, R 1s , R 2s , R 11s , R 12s , R 13s , and / or R14s The structure of any heteroatom ligand depicted herein and / or each R of any heteroatom ligand chromium compound complex depicted herein, 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may independently be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group; alternatively, an alkyl group or a substituted alkyl group; alternatively, a cycloalkyl group or a substituted cycloalkyl group; alternatively, an aryl group or a substituted aryl group; alternatively, an aralkyl group or a substituted aralkyl group; or alternatively, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The structure of any heteroatom ligand depicted herein and / or each R of any heteroatom ligand chromium compound complex depicted herein, 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may independently be an alkyl group, alternatively a substituted alkyl group, alternatively a cycloalkyl group, alternatively a substituted cycloalkyl group, alternatively an aryl group, alternatively a substituted aryl group, alternatively an aralkyl group, or alternatively a substituted aralkyl group.

[0146] In any embodiment disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The alkyl groups are independently C1 to C 20 , C1~C 10or a C1-C5 alkyl group. In any embodiment disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The substituted alkyl groups are independently C1-C 20 , C1~C 10 or a C1-C5 substituted alkyl group. In any of the embodiments disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The cycloalkyl groups are independently C4 to C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The substituted cycloalkyl groups are independently C4-C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The aryl groups are independently C6 to C 20 , C6~C 15 , or C6~C 10 In any embodiment disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The substituted aryl groups are independently C6-C 20 , C6~C 15 , or C6~C 10In any embodiment disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The aralkyl groups are independently C7-C 20 , C7~C 15 , or C7~C 10 In any embodiment disclosed herein, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The substituted aralkyl groups are independently C7 to C 20 , C7~C 15 , or C7~C 10 It may be a substituted aralkyl group. Each substituent of the substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), and / or substituted aralkyl group (general or specific) may be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarboxy groups, and substituent hydrocarboxy groups are independently defined by R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may be used without limitation to further illustrate the substituents (general or specific) that may be used as groups.

[0147] In some embodiments, each R 1s , R 2s , R 11s , R 12s, R 13s , and / or R 14s can independently be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group, or alternatively a methyl group, an ethyl group, an iso-propyl (2-propyl) group, a tert-butyl (2-methyl-2-propyl) group, or a neopentyl (2,2-dimethyl-1-propyl) group. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The alkyl groups that may be utilized as R may be independently substituted. Each substituent of the substituted alkyl group may independently be a halogen or a hydrocarboxy group, alternatively a halogen, or alternatively a hydrocarboxy group. The substituent halogen and the substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogen and substituent hydrocarboxy groups are independently disclosed herein. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may be used without limitation to further illustrate the substituted alkyl groups (general or specific) that may be utilized as substituted alkyl groups.

[0148] In some embodiments, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14smay independently be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group; alternatively, a cyclopentyl group or a substituted cyclopentyl group; alternatively, a cyclohexyl group or a substituted cyclohexyl group; alternatively, a cyclopentyl group, alternatively, a substituted cyclopentyl group, alternatively, a cyclohexyl group, or alternatively, a substituted cyclohexyl group. In certain embodiments, when present in any heteroatomic ligand described herein, any heteroatomic ligand of a heteroatomic ligand chromium compound complex described herein, the formula or structure of any heteroatomic ligand provided herein, and / or the structure of any heteroatomic ligand chromium compound complex provided herein, R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The substituted cycloalkyl groups that may be utilized for any of R may independently be 2-substituted cyclohexyl, 2,6-disubstituted cyclohexyl, 2-substituted cyclopentyl, or 2,5-disubstituted cyclopentyl, alternatively 2-substituted cyclohexyl or 2,6-disubstituted cyclohexyl, alternatively 2-substituted cyclopentyl or 2,5-disubstituted cyclopentyl, alternatively 2-substituted cyclohexyl or 2-substituted cyclopentyl, or alternatively 2,6-disubstituted cyclohexyl or 2,5-disubstituted cyclopentyl. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14sOne or more substituents of a polysubstituted cycloalkyl group utilized as R can be the same or different, alternatively, all of the substituents of a polysubstituted cycloalkyl group can be the same, or alternatively, all of the substituents of a polysubstituted cycloalkyl group can be different. Each substituent of a substituted cycloalkyl group (general or specific) having a specified number of ring carbon atoms can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently selected from R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may be used without limitation to further illustrate the substituted cycloalkyl groups (general or specific) that may be used as substituted cycloalkyl groups.

[0149] In a non-limiting embodiment, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may independently be a cyclohexyl group, a 2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group, or alternatively a cyclopentyl group, a 2-alkylcyclopentyl group, or a 2,5-dialkylcyclopentyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14The terms "R" and "R" may be used without limitation to further illustrate alkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups (general or specific), alkylcyclopentyl groups (general or specific), and / or dialkylcyclopentyl groups (general or specific). Generally, the alkyl substituents of a disubstituted cyclohexyl or cyclopentyl group can be the same, or alternatively, the alkyl substituents can be different. In some non-limiting aspects, each R, when present in any heteroatom ligand described herein, any heteroatom ligand of a heteroatom ligand chromium compound complex described herein, the formula or structure of any heteroatom ligand provided herein, and / or the structure of any heteroatom ligand chromium compound complex provided herein, ... 1s , R 2s , R 11s , R 12s , R 13s , and R 14s may independently be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-di-tert-butylcyclohexyl, alternatively 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, or 2-tert-butylcyclohexyl, or alternatively 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-di-tert-butylcyclohexyl.

[0150] In some embodiments, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14smay independently be a phenyl group or a substituted phenyl group, alternatively a phenyl group, or alternatively a substituted phenyl group. In certain embodiments, each R that may be utilized for a substituted phenyl group when present in any heteroatom ligand described herein, any heteroatom ligand of a heteroatom-ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or the structure of any heteroatom-ligand chromium compound complex provided herein. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s are independently 2-substituted phenyl, 3-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, 2,6-disubstituted phenyl, 3,5-disubstituted phenyl, or 2,4,6-trisubstituted phenyl; alternatively, 2-substituted phenyl, 4-substituted phenyl, 2,4-disubstituted phenyl, or 2,6-disubstituted phenyl; alternatively, 3-substituted phenyl or 3,5-disubstituted phenyl; alternatively, 2-substituted phenyl or 4-substituted phenyl; alternatively, 2,4-disubstituted phenyl or 2,6-disubstituted phenyl; alternatively, 2-substituted phenyl, alternatively, 3-substituted phenyl, alternatively, 4-substituted phenyl, alternatively, 2,4-disubstituted phenyl, alternatively, 2,6-disubstituted phenyl, alternatively, 3,5-disubstituted phenyl, or alternatively, 2,4,6-trisubstituted phenyl. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14sThe one or more substituents of a polysubstituted phenyl group utilized as R can be the same or different; alternatively, all the substituents can be the same, or alternatively, all the substituents can be different. Each substituent of a substituted phenyl group (generic or specific) can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (generic and specific), and substituent hydrocarboxy groups (generic and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may be used without limitation to further illustrate the substituted phenyl groups (general or specific) that may be utilized as phenyl groups.

[0151] In a non-limiting embodiment, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14smay independently be a phenyl group, a 2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively a 2-alkylphenyl group or a 4-alkylphenyl group, alternatively a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group; alternatively a 3-alkylphenyl group or a 3,5-dialkylphenyl group; alternatively a 2-alkylphenyl group or a 2,6-dialkylphenyl group; or alternatively a 2,4,6-trialkylphenyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s The term "alkyl-substituted phenyl" can be used without limitation to further illustrate any alkyl-substituted phenyl group that can be utilized as an alkyl group. Generally, the alkyl substituents of a dialkylphenyl group (general or specific) or a trialkylphenyl group (general or specific) can be the same, or alternatively, the alkyl substituents can be different. In some non-limiting aspects, each R, when present in any heteroatom ligand described herein, any heteroatom ligand of a heteroatom-ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or the structure of any heteroatom-ligand chromium compound complex provided herein, can be used without limitation to further illustrate any alkyl-substituted phenyl group that can be utilized as an alkyl group. In some non-limiting aspects, the term "alkyl-substituted phenyl" ... 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14sare independently phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl, or 2,4,6-trimethylphenyl; alternatively phenyl, 2-methylphenyl, 2-ethylphenyl, 2-n-propylphenyl, 2-isopropylphenyl, or 2-tert-butylphenyl; or alternatively phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-n-propylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2-isopropyl-6-methylphenyl, or 2,4,6-trimethylphenyl.

[0152] In a non-limiting embodiment, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s can independently be a phenyl group, a 2-alkoxyphenyl group, or a 4-alkoxyphenyl group. In some non-limiting embodiments, each R, when present in any heteroatom ligand described herein, any heteroatom ligand of a heteroatom-ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or the structure of any heteroatom-ligand chromium compound complex provided herein, 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14scan be independently a phenyl group, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, a 2-tert-butoxyphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group, alternatively a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a 2-tert-butoxyphenyl group, or alternatively a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group. 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s can independently be a phenyl group, a 2-halophenyl group, a 4-halophenyl group, or a 2,6-dihalophenyl group. In general, the halides of the dihalophenyl groups can be the same, or alternatively, the halides can be different. In some embodiments, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s can independently be a phenyl group, a 2-fluorophenyl group, a 4-fluorophenyl group, or a 2,6-difluorophenyl group.

[0153] In some embodiments, each R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14smay independently be a benzyl group or a substituted benzyl group, alternatively a benzyl group, or alternatively a substituted benzyl group. Each substituent of a substituted benzyl group (generic or specific) may independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group, alternatively a halogen or a hydrocarbyl group, alternatively a halogen or a hydrocarboxy group, alternatively a hydrocarbyl group or a hydrocarboxy group, alternatively a halogen, alternatively a hydrocarbyl group, or alternatively a hydrocarboxy group. Substituent halogens, substituent hydrocarbyl groups (generic and specific), and substituent hydrocarboxy groups (generic and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 1s , R 2s , R 11s , R 12s , R 13s , and / or R 14s may be used without limitation to further illustrate the substituted benzyl groups (general or specific) that may be used as

[0154] In a further embodiment, two geminal R 1s , two geminal R 2s , Germinal R 11s and R 12s , and / or Germinal R 13s and R 14s may independently be joined to form a ring or ring system containing the heteroatoms to which they are attached. Two geminal R 1s The bond of L 11s Two geminal R 2s The bond of L 22s It can be specified as: Geminal R 11s and R 12s The bond of L 12s It can be specified as: Geminal R 13s and R 14s The bond of L 34s In some embodiments, L 11s , L 22s , L 12s , and / or L 34smay independently be an organylene group, alternatively an organylene group consisting of an inert functional group, alternatively a hydrocarbylene group, or alternatively an alkylene group. 11s , L 22s , L 12s , and / or L 34s The organylene groups are independently C4-C 30 , C4~C 20 , C4~C 15 , or C4~C 10 In some embodiments, L, when present, comprises an inert functional group. 11s , L 22s , L 12s , and / or L 34s The organylene groups are independently C4-C 30 , C4~C 20 , C4~C 15 , or C4~C 10 In other embodiments, when present, L 11s , L 22s , L 12s , and / or L 34s The hydrocarbyl groups are independently C4 to C 30 , C4~C 20 , C4~C 15 , or C4~C 10 In a further aspect, when present, L 11s , L 22s , L 12s , and / or L 34s The alkylene groups are independently C4 to C 30 , C4~C 20 , C4~C 15 , or C4~C 10 In some embodiments, when present, L 12s and / or L 34smay independently be a but-1,4-ylene group, a 1,4-diphenylbut-1,4-ylene group, a 1,4-di(2-methylphenyl)but-1,4-ylene group, a 1,4-di(4-methylphenyl)but-1,4-ylene group, a 1,4-di(4-t-butylphenyl)but-1,4-ylene group, a 1,4-di(3,5-dimethylphenyl)but-1,4-ylene group, a pent-1,4-ylene group, a 1-phenylpent-1,4-ylene group, a 4-phenylpent-1,4-ylene group, a hex-2,5-ylene group, a 2,2′-biphenylene group, a 2,2′-(methanediyl)diphenylene group, or a 2,2′-(1,2-ethanediyl)diphenylene group.

[0155] In general, R 5s The structure of any heteroatom ligand depicted herein having a group and the R of any heteroatom ligand chromium compound complex depicted herein 5s may be an organyl group, alternatively an organyl group consisting of an inert functional group, or alternatively a hydrocarbyl group. 5s Organyl groups are C1-C 20 , C1~C 15 , C1~C 10 or a C1-C5 organyl group. In some embodiments, R 5s The organyl group is an inert functional group consisting of C1-C 20 , C1~C 15 , C1~C 10 , or a C1-C5 organyl group. 5s The hydrocarbyl group is C1 to C 20 , C1~C 15 , C1~C 10 , or a C1 to C5 hydrocarbyl group.

[0156] In some embodiments, R 5s The structure of any heteroatom ligand depicted herein having a group and the R of any heteroatom ligand chromium compound complex depicted herein 5smay be an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a substituted aralkyl group, or may be an alkyl group or a substituted alkyl group, alternatively a cycloalkyl group or a substituted cycloalkyl group, alternatively an aryl group or a substituted aryl group, alternatively an aralkyl group or a substituted aralkyl group, or alternatively an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. 5s The structure of any heteroatom ligand depicted herein having a group and the R of any heteroatom ligand chromium compound complex depicted herein 5s may be an alkyl group, alternatively a substituted alkyl group, alternatively a cycloalkyl group, alternatively a substituted cycloalkyl group, alternatively an aryl group, alternatively a substituted aryl group, alternatively an aralkyl group, or alternatively a substituted aralkyl group. 5s The alkyl group is C1 to C 20 , C1~C 15 , or C1~C 10 In any embodiment disclosed herein, R 5s The substituted alkyl group is C1-C 20 , C1~C 15 , or C1~C 10 In any of the embodiments disclosed herein, R 5s The cycloalkyl group is C4-C 20 , C4~C 15 , or C4~C 10 In any embodiment disclosed herein, R 5s The substituted cycloalkyl group is C4-C 20 , C4to, or C4~C 10 In any embodiment disclosed herein, R 5s The aryl group is C6-C 20 , C6~C 15 , or C6~C 10 In any embodiment disclosed herein, R 5sThe substituted aryl group is C6-C 20 , C6~C 15 , or C6~C 10 In any of the embodiments disclosed herein, R 5s Aralkyl groups are C7-C 20 , C7~C 15 , or C7~C 10 In any embodiment disclosed herein, R 5s The substituted aralkyl group is C7-C 20 , C7~C 15 , or C7~C 10 It may be a substituted aralkyl group. Each substituent of the substituted alkyl group (general or specific), substituted cycloalkyl group (general or specific), substituted aryl group (general or specific), and / or substituted aralkyl group (general or specific) may be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxyl group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. The substituent halogens, hydrocarbyl groups (general and specific), and substituent hydrocarboxy groups (general and specific) are independently disclosed herein. These substituent halogens, substituent hydrocarbyl groups, and substituent hydrocarboxy groups are independently defined by R 5s may be used without limitation to further illustrate the substituents (general or specific) that may be used as groups.

[0157] In some embodiments, R 5sis methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; alternatively, methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), n-butyl (1-butyl), sec-butyl (2-butyl), isobutyl (2-methyl-1-propyl), tert-butyl (2-methyl-2-propyl), n-pentyl (1-pentyl), 2-pentyl In some embodiments, R may be a methyl group, a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl(2-methyl-2-butyl) group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl(2,2-dimethyl-1-propyl) group, or alternatively a methyl group, an ethyl group, an iso-propyl(2-propyl) group, a tert-butyl(2-methyl-2-propyl) group, or a neopentyl(2,2-dimethyl-1-propyl) group. 5s The alkyl group may be substituted. 5s Each substituent of the substituted alkyl group may independently be a halogen or a hydrocarboxy group, alternatively a halogen, or alternatively a hydrocarboxy group. The substituent halogen and substituent hydrocarboxy groups (general and specific) are described independently herein, and these substituents are defined by R 5s These groups may be used without limitation to further illustrate the substituted alkyl groups (general or specific) that may be utilized as R 5s may be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, a substituted cyclohexyl group, alternatively a cyclopentyl group or a substituted cyclopentyl group, or alternatively a cyclohexyl group or a substituted cyclohexyl group. 5scan be a 2-substituted cyclohexyl group, a 2,6-disubstituted cyclohexyl group, a 2-substituted cyclopentyl group, or a 2,5-disubstituted cyclopentyl group, alternatively a 2-substituted cyclohexyl group or a 2,6-disubstituted cyclohexyl group, alternatively a 2-substituted cyclohexyl group or a 2,6-disubstituted cyclohexyl group, alternatively a 2-substituted cyclopentyl group or a 2,5-disubstituted cyclopentyl group, alternatively a 2-substituted cyclohexyl group or a 2-substituted cyclopentyl group, or alternatively a 2,6-disubstituted cyclohexyl group or a 2,5-disubstituted cyclopentyl group. 5s One or more substituents of a polysubstituted cycloalkyl group utilized as R can be the same or different, alternatively, all of the substituents of a polysubstituted cycloalkyl group can be the same, or alternatively, all of the substituents of a polysubstituted cycloalkyl group can be different. Each substituent of a cycloalkyl group (general or specific) having a specified number of ring carbon atoms can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. The substituent halogen, the substituent hydrocarbyl group (general and specific), and the substituent hydrocarboxy group (general and specific) are described independently herein, and these substituents are defined by R 5s may be used without limitation to further illustrate the substituted cycloalkyl groups (general or specific) that may be used as substituted cycloalkyl groups.

[0158] In a non-limiting embodiment, R 5s may be a cyclohexyl group, a 2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group, or alternatively a cyclopentyl group, a 2-alkylcyclopentyl group, or a 2,5-dialkylcyclopentyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 5scan be used without limitation to further illustrate alkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups (general or specific), alkylcyclopentyl groups (general or specific), and / or dialkylcyclopentyl groups (general or specific). Generally, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl groups can be the same, or alternatively, the alkyl substituents can be different. In some non-limiting aspects, the R groups provided herein can be used ... 5s The structure of the heteroatom ligand, and / or the structure of any of the heteroatom ligand chromium compound complexes provided herein, can be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group. 5s can be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, or a 2-tert-butylcyclohexyl group, or alternatively a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group. 5s The structure of the heteroatom ligand, and / or the structure of any heteroatom ligand chromium compound complex provided herein, can be a cyclopentyl group, a 2-methylcyclopentyl group, a cyclohexyl group, or a 2-methylcyclohexyl group, alternatively a cyclopentyl group or a cyclohexyl group, or alternatively a 2-methylcyclopentyl group or a 2-methylcyclohexyl group.

[0159] In some embodiments, R 5s may be a phenyl group or a substituted phenyl group, alternatively a phenyl group, or alternatively a substituted phenyl group. In some embodiments, R 5smay be a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenyl group or a 4-substituted phenyl group; alternatively, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group; alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group; alternatively, a 2-substituted phenyl group, alternatively a 4-substituted phenyl group, alternatively a 2,4-disubstituted phenyl group, alternatively a 2,6-disubstituted phenyl group, or alternatively a 2,4,6-trisubstituted phenyl group. 5s The one or more substituents of a polysubstituted phenyl group utilized as R can be the same or different, alternatively, all the substituents can be the same, or alternatively, all the substituents can be different. Each substituent of a substituted phenyl group (generic or specific) can independently be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. The substituent halogen, substituent hydrocarbyl group (generic and specific), and substituent hydrocarboxy group (generic and specific) are independently described herein, and these substituents are defined by R 5s may be used without limitation to further illustrate the substituted phenyl groups (general or specific) that may be utilized as phenyl groups.

[0160] In a non-limiting embodiment, R 5s may be a phenyl group, a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group, alternatively a 2-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group. The alkyl substituents (general and specific) are described independently herein, and these alkyl substituents are substituted by R 5sThe term "alkyl-substituted phenyl" can be used without limitation to further describe any alkyl-substituted phenyl group that can be utilized as R. Generally, the alkyl substituents of a dialkylphenyl group (general or specific) or a trialkylphenyl group (general or specific) can be the same, or alternatively, the alkyl substituents can be different. In some non-limiting embodiments, R 5s may be a phenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a 2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a 2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a 2,4,6-trimethylphenyl group, alternatively a phenyl group, a 2-methylphenyl group, a 2,6-dimethylphenyl group, or a 2,4,6-trimethylphenyl group.

[0161] In general, L 2s Any heteroatom ligand having a group and / or any heteroatom ligand chromium compound complex L 2s may be an organylene group, alternatively an organylene group consisting of an inert functional group, alternatively a hydrocarbylene group, or alternatively an alkylene group. 2s The organylene group is C1-C 20 , C1~C 15 , or C1~C 10 In some embodiments, L may be an organylene group. 2s The organylene group is a C1-C 20 , C1~C 15 , or C1~C 10 In some embodiments, L 2s The alkylene group is C1 to C 20 , C1~C 15 , or C1~C 10 It may be an alkylene group.

[0162] In one embodiment, L 2sAny heteroatom ligand having a group and / or any heteroatom ligand chromium compound complex L 2s is -(CR P R P’ ) m -, wherein each R P and R P’ may independently be hydrogen, methyl, ethyl, propyl, isopropyl, or butyl groups, and m may be an integer from 1 to 12. In some embodiments, L 2s Any heteroatom ligand having a group and / or any heteroatom ligand chromium compound complex L 2s may be a methylene group (-CH-), an eth-1,2-ylene group (-CHCH-), a prop-1,3-ylene group (-CHCHCH-), a prop-1,2-ylene group (-CH(CH)CH-), a prop-2,2-ylene group (-C(CH)-), a but-1,4-ylene group (-CHCHCHCHCH-), or a 2-methylprop-1,3-ylene group (-CHCH(CH)CH-), or alternatively a methylene group (-CH-), an eth-1,2-ylene group (-CHCH-), or a prop-1,2-ylene group (-CH(CH)CH-).

[0163] In one embodiment, L 2s Any heteroatom ligand having a group and / or any heteroatom ligand chromium compound complex L 2sare 1,2-cyclohexylene, substituted 1,2-cyclohexylene, 1,3-cyclohexylene, substituted 1,3-cyclohexylene, 1,4-cyclohexylene, substituted 1,4-cyclohexylene, 3,3'-bicyclohexylene, substituted 3,3'-bicyclohexylene, 4,4'-bicyclohexylene, substituted 4,4'-bicyclohexylene, bis(3-cyclohexylene)methane, substituted bis(3-cyclohexylene)methane, bis(4-cyclohexylene)methane, substituted bis(4-cyclohexylene)methane, 1,2-bis(3-cyclohexylene)ethane, substituted 1,2-bis(3- 1,2-bis(4-cyclohexylene)ethane, 1,2-bis(4-cyclohexylene)ethane, substituted 1,2-bis(4-cyclohexylene)ethane, 1,2-bis(3-cyclohexylene)propane, substituted 1,2-bis(3-cyclohexylene)propane, 1,2-bis(4-cyclohexylene)propane, substituted 1,2-bis(4-cyclohexylene)propane, 2,2-bis(3-cyclohexylene)propane, substituted 2,2-bis(3-cyclohexylene)propane, 2,2-bis(4-cyclohexylene)propane, or substituted 2,2-bis(4-cyclohexylene)propane. 2s Any heteroatom ligand having a group and / or any heteroatom ligand chromium compound complex L 2s can be a substituted 1,2-cyclohexylene, a substituted 1,3-cyclohexylene, a substituted 1,4-cyclohexylene, a substituted 3,3'-bicyclohexylene, a substituted 4,4'-bicyclohexylene, a substituted bis(3-cyclohexylene)methane, a substituted bis(4-cyclohexylene)methane, a substituted 1,2-bis(3-cyclohexylene)ethane, a substituted 1,2-bis(4-cyclohexylene)ethane, a substituted 1,2-bis(3-cyclohexylene)propane, a substituted 1,2-bis(4-cyclohexylene)propane, a substituted 2,2-bis(3-cyclohexylene)propane, or a substituted 2,2-bis(4-cyclohexylene)propane. 2sEach substituent of the substituted cyclohexylene, substituted bis(cyclohexylene)methane, substituted bis(cyclohexylene)ethane, or substituted 1,2-bis(3-cyclohexylene)propane that may be utilized as L may be a hydrocarbyl group. The substituents (general and specific) are disclosed independently herein, and L 2s To further illustrate, without limitation, substituted cyclohexylene (general or specific), substituted bis(cyclohexylene)methane (general or specific), substituted bis(cyclohexylene)ethane (general or specific), or substituted 1,2-bis(3-cyclohexylene)propane (general or specific) may be utilized.

[0164] In one embodiment, L 2s Any heteroatom ligand having a group and / or any heteroatom ligand chromium compound complex L 2s are 1,2-phenylene, substituted 1,2-phenylene, 1,3-phenylene, substituted 1,3-phenylene, 1,4-phenylene, substituted 1,4-phenylene, 3,3'-biphenylene, substituted 3,3'-biphenylene, 4,4'-biphenylene, substituted 4,4'-biphenylene, bis(3-phenylene)methane, substituted bis(3-phenylene)methane, bis(4-phenylene)methane, substituted bis(4-phenylene)methane, 1,2-bis(3-phenylene)ethane, substituted 1,2-bis(3-phenylene) It can be ethane, 1,2-bis(4-phenylene)ethane, substituted 1,2-bis(4-phenylene)ethane, 1,2-bis(3-phenylene)propane, substituted 1,2-bis(3-phenylene)propane, 1,2-bis(4-phenylene)propane, substituted 1,2-bis(4-phenylene)propane, 2,2-bis(3-phenylene)propane, substituted 2,2-bis(3-phenylene)propane, 2,2-bis(4-phenylene)propane, or substituted 2,2-bis(4-phenylene)propane. 2s Any heteroatom ligand having a group and / or any heteroatom ligand chromium compound complex L 2scan be a substituted 1,2-phenylene, substituted 1,3-phenylene, substituted 1,4-phenylene, substituted 3,3'-biphenylene, substituted 4,4'-biphenylene, substituted bis(3-phenylene)methane, substituted bis(4-phenylene)methane, substituted 1,2-bis(3-phenylene)ethane, substituted 1,2-bis(4-phenylene)ethane, substituted 1,2-bis(3-phenylene)propane, substituted 1,2-bis(4-phenylene)propane, substituted 2,2-bis(3-phenylene)propane, or substituted 2,2-bis(4-phenylene)propane. 2s Each substituent of the substituted phenylene (general or specific), substituted biphenylene (general or specific), substituted bis(phenylene)methane (general or specific), substituted bis(phenylene)ethane (general or specific), and / or substituted bis(phenylene)propane (general or specific) that may be utilized as L may be a hydrocarbyl group. The substituent hydrocarbyl groups (general and specific) are disclosed independently herein, and L 2s To further illustrate, without limitation, substituted phenylenes (general or specific), substituted biphenylenes (general or specific), substituted bis(phenylene)methanes (general or specific), substituted bis(phenylene)ethanes (general or specific), and / or substituted bis(phenylene)propanes (general or specific) may be used.

[0165] In general, L 3s and / or L 4s Any heteroatom ligand having a group and / or any heteroatom ligand chromium compound complex L 3s and / or L 4s may independently be an organylene group, alternatively an organylene group consisting of an inert functional group, alternatively a hydrocarbylene group, or alternatively an alkylene group. 3s and / or L 4s The organylene groups are independently C1-C 20 , C1~C 15 , or C1~C 10 In some embodiments, L may be an organylene group. 3s and / or L4s The organylene groups are independently C1-C2 groups consisting of inert functional groups. 20 , C1~C 15 , or C1~C 10 In some embodiments, L 3s and / or L 4s The hydrocarbylene groups are independently C1 to C 20 , C1~C 15 , or C1~C 10 In some embodiments, L 3s and / or L 4s The alkylene groups are independently C1 to C 20 , C1~C 15 , or C1~C 10 It may be an alkylene group.

[0166] In one embodiment, L 3s and / or L 4s The structure of any heteroatom ligand having a group and / or the L of any heteroatom ligand chromium compound complex 3s and / or L 4s are independently -(CR P R P’ ) m -, wherein each R P and R P’ may independently be hydrogen, methyl, ethyl, propyl, isopropyl, or butyl groups, and m may be an integer from 1 to 12. In some embodiments, L 3s and / or L 4s The structure of any heteroatom ligand having a group and / or the L of any heteroatom ligand chromium compound complex 3s and / or L 4sare independently a methylene group (-CH2-), an eth-1,2-ylene group (-CH2CH2-), an ethene-1,2-ylene group (-CH=CH-), a prop-1,3-ylene group (-CH2CH2CH2-), a prop-1,2-ylene group (-CH(CH3)CH2-), a prop-2,2-ylene group (-C(CH3)2-), a 1-methylethene-1,2-ylene group (-C(CH3)=CH-), a but-1,4-ylene group (-CH2CH2CH2-CH2-), a but- 1,3-ylene (-CH2CH2CH(CH3)-), but-2,3-ylene (-CH(CH3)CH(CH3)-), but-2-en-2,3-ylene (-C(CH3)C(CH3)-), 3-methylbut-1,3-ylene (-CH2CH2C(CH3)2-), 1,2-cyclopentylene, 1,2-cyclohexylene, or phen-1,2-ylene, alternatively methylene (-CH2-), eth-1,2-ylene (-CH2C H2-), prop-1,3-ylene group (-CH2CH2CH2-), prop-1,2-ylene group (-CH(CH3)CH2-), prop-2,2-ylene group (-C(CH3)2-), but-1,4-ylene group (-CH2CH2CH2-CH2-), but-1,3-ylene group (-CH2CH2CH(CH3)-), but-2,3-ylene group (-CH(CH3)CH(CH3)-), 1,2-cyclopentylene group, 1,2-cyclohexylene group, or fluorene group It may be a phen-1,2-ylene group, or alternatively an eth-1,2-ylene group (-CH2CH2-), a prop-1,3-ylene group (-CH2CH2CH2-), a prop-1,2-ylene group (-CH(CH3)CH2-), a but-1,3-ylene group (-CH2CH2CH(CH3)-), a but-2,3-ylene group (-CH(CH3)CH(CH3)-), a 1,2-cyclopentylene group, a 1,2-cyclohexylene group, or a phen-1,2-ylene group.

[0167] Various aspects described herein refer to non-hydrogen substituents, such as halogen (or halo, halide), hydrocarbyl, hydrocarboxy, alkyl, and / or alkoxy substituents. In certain embodiments, each non-hydrogen substituent of any aspect requiring a substituent can be a halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen, alternatively, a hydrocarbyl group, or alternatively, a hydrocarboxy group. Each hydrocarbyl substituent is independently C1-C6 10 Each hydrocarboxy substituent may independently be a C1-C5 hydrocarbyl group, or alternatively a C1-C5 hydrocarbyl group. 10 A hydrocarboxy group, or alternatively a C1-C5 hydrocarboxy group. Each halide substituent may independently be fluoride, chloride, bromide, or iodide, alternatively fluoride or chloride, alternatively fluoride, alternatively chloride, alternatively bromide, or alternatively iodide.

[0168] In some embodiments, any hydrocarbyl substituents may independently be alkyl, aryl, or aralkyl groups; alternatively, alkyl groups, alternatively, aryl groups, or alternatively, aralkyl groups. In some embodiments, any alkyl substituents may independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, tert-pentyl, 3-methyl-1-butyl, 3-methyl-2-butyl, or neo-pentyl groups; alternatively, methyl, ethyl, isopropyl, tert-butyl, or neo-pentyl groups; alternatively, methyl, alternatively, ethyl, alternatively, isopropyl, alternatively, tert-butyl, or alternatively, neo-pentyl groups. In some embodiments, any aryl substituent may independently be a phenyl group, a tolyl group, a xylyl group, or a 2,4,6-trimethylphenyl group, alternatively a phenyl group, alternatively a tolyl group, alternatively a xylyl group, or alternatively a 2,4,6-trimethylphenyl group. In some embodiments, any aralkyl substituent may independently be a benzyl group or an ethylphenyl group (2-phenyleth-1-yl or 1-phenyleth-1-yl), alternatively a benzyl group, alternatively an ethylphenyl group, alternatively a 2-phenyleth-1-yl group, or alternatively a 1-phenyleth-1-yl group.

[0169] In some embodiments, any hydrocarboxy substituents may independently be an alkoxy group, an aryloxy group, or an aralkoxy group, alternatively an aryloxy group, or an aralkoxy group. In some embodiments, any alkoxy substituents may independently be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, tert-pentoxy, 3-methyl-1-butoxy, 3-methyl-2-butoxy, or neo-pentoxy; alternatively, methoxy, ethoxy, isopropoxy, tert-butoxy, or neo-pentoxy; alternatively, methoxy, alternatively ethoxy, alternatively isopropoxy, alternatively tert-butoxy, or alternatively neo-pentoxy. In some embodiments, any aryloxy substituents may independently be a phenoxy group, a toloxy group, a xyloxy group, or a 2,4,6-trimethylphenoxy group, alternatively a phenoxy group, alternatively a toloxy group, alternatively a xyloxy group, or alternatively a 2,4,6-trimethylphenoxy group. In some embodiments, any aralkoxy substituents may independently be a benzoxy group.

[0170] Generally, the transition metal of a heteroatom-ligand transition metal compound complex or transition metal compound, MX pcan be any transition metal atom. In certain embodiments, the transition metal atom of the transition metal compound can comprise or consist essentially of a Group 3-12, Group 4-10, Group 6-9, or Group 7-8 transition metal. In some embodiments, the transition metal atom of the transition metal compound can comprise or consist essentially of a Group 4 transition metal, alternatively a Group 5 transition metal, alternatively a Group 6 transition metal, alternatively a Group 7 transition metal, alternatively a Group 8 transition metal, alternatively a Group 9 transition metal, or alternatively a Group 10 transition metal. In certain embodiments, the transition metal atom of the transition metal compound may comprise or consist essentially of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, platinum, copper, or zinc; alternatively, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, iron, cobalt, nickel, palladium, or platinum; alternatively, chromium, iron, cobalt, or nickel; alternatively, titanium, zirconium, or hafnium; alternatively, vanadium or niobium; alternatively, chromium, molybdenum, or tungsten; alternatively, iron or cobalt; or alternatively, nickel, palladium, platinum, copper, or zinc. In other embodiments, the metal salt may comprise titanium, alternatively zirconium, alternatively hafnium, alternatively vanadium, alternatively niobium, alternatively tantalum, alternatively chromium, alternatively molybdenum, alternatively tungsten, alternatively manganese, alternatively iron, alternatively cobalt, alternatively nickel, alternatively palladium, alternatively platinum, alternatively copper, or alternatively zinc. Generally, the transition metal atom MX of the heteroatom-ligand transition metal compound complex or transition metal compound p may have any positive oxidation state that a transition metal atom can have. In certain embodiments, the transition metal atom may have an oxidation state of +2 to +6, alternatively +2 to +4, or alternatively +2 to +3. In some embodiments, the transition metal atom MX of the transition metal compound p may have an oxidation state of +1, alternatively +2, alternatively +3, or alternatively +4.

[0171] Generally, the chromium compounds of the chromium compounds or heteroatom-ligand chromium compound complexes described herein have the formula CrX p where X represents a monoanionic ligand and p(general heteroatom ligand formula [(HetLig)CrX q L r ] 3-q The q) in (A) represents the number of monoanionic ligands in the chromium compound (and the oxidation state of chromium). The monoanionic ligand (X) and p are independent elements of the chromium compounds of the chromium compounds or heteroatom-ligand chromium compound complexes described herein and are described independently herein. The independent descriptions of the monoanionic ligand (X) and p may be utilized in any combination, without limitation, to further describe the chromium compounds of the chromium compounds or heteroatom-ligand chromium compound complexes described herein.

[0172] Generally, chromium compounds (CrX p The chromium atom of the chromium compound (CrX) can have any positive oxidation state that a chromium atom can have. In some embodiments, the chromium atom can have an oxidation state of +2 to +6, alternatively +2 to +4, or alternatively +2 to +3. In some embodiments, the chromium compound (CrX) can have any positive oxidation state that a chromium atom can have. In some embodiments, the chromium atom of ... p The chromium atom in ) may have an oxidation state of +1, alternatively +2, alternatively +3, or alternatively +4.

[0173] The monoanion (X) of the chromium compound can be any monoanion. In some embodiments, the monoanion (X) can be a halide, carboxylate, β-diketonate, hydrocarboxylate, nitrate, or chlorate. In some embodiments, the monoanion (X) can be a halide, carboxylate, β-diketonate, or hydrocarboxylate. In any embodiment, the hydrocarboxylate can be an alkoxide, aryloxide, or aralkoxide. In general, hydrocarboxylates (and subclasses of hydrocarboxylates) are anionic analogs of the hydrocarboxy group. In other embodiments, the monoanion (X) can be a halide, carboxylate, β-diketonate, or alkoxide, or alternatively a halide or β-diketonate. In other embodiments, the monoanion (X) can be a halide, alternatively a carboxylate, alternatively a β-diketonate, alternatively a hydrocarboxylate, alternatively an alkoxide, or alternatively an aryloxide. Generally, when the heteroatomic ligand of the heteroatomic-ligand chromium compound complex is a neutral heteroatomic ligand, the number of monoanions (p) can be equal to the oxidation state of the chromium atom. When the heteroatomic ligand of the heteroatomic-ligand chromium compound complex is an anionic heteroatomic ligand, the number of monoanions (p) can be equal to the oxidation state of the chromium atom minus 1. In some embodiments, the number of monoanions can be 2 to 6, alternatively 2 to 4, alternatively 2 to 3, alternatively 1, alternatively 2, alternatively 3, or alternatively 4.

[0174] Generally, each halide of the chromium compound can independently be fluorine, chlorine, bromine, or iodine, or alternatively chlorine, bromine, or iodine. In some embodiments, each halide monoanion of the chromium compound can be chlorine, alternatively bromine, or alternatively iodine.

[0175] Generally, each carboxylate of the chromium compound is independently C1-C 20 Carboxylate, or alternatively C1-C 10In some embodiments, each carboxylate of the chromium compound can independently be acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate, or alternatively pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate. In some embodiments, each carboxylate of the chromium compound is independently acetate, propionate, n-butyrate, valerate (n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate), alternatively valerate (n-pentanoate) ), neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively capronate (n-hexanoate), alternatively n-heptanoate, alternatively caprylate (n-octanoate), or alternatively 2-ethylhexanoate. In some embodiments, the carboxylate of the chromium compound can be triflate (trifluoroacetate).

[0176] Generally, each β-diketonate of the chromium compound may independently be any C1-C 20 β-diketonate, or alternatively any C1-C 10In some embodiments, each β-diketonate of the chromium compound can independently be an acetylacetonate (i.e., 2,4-pentanedionate), a hexafluoroacetylacetonate (i.e., 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), or a benzoylacetonate, alternatively an acetylacetonate, alternatively a hexafluoroacetylacetonate, or alternatively a benzoylacetonate.

[0177] Generally, each hydrocarboxylate of the chromium compound may independently be any C1-C 20 Hydroxycarboxylate, or alternatively any C1-C 10 In some embodiments, each hydrocarboxylate of the chromium compound can be independently a C1-C 20 Alkoxides, alternatively C1-C 10 Alkoxides, alternatives C6-C 20 Aryloxide, or alternatively C6-C 10 In some embodiments, each alkoxide of the chromium compound can independently be methoxide, ethoxide, propoxide, or butoxide; alternatively, methoxide, ethoxide, isopropoxide, or tert-butoxide; alternatively, methoxide, alternatively, ethoxide, alternatively, isopropoxide, or alternatively, tert-butoxide. In some embodiments, the aryloxide can be phenoxide.

[0178] In some non-limiting embodiments, the chromium compound and / or the chromium compound of the heteroatom-ligand chromium compound complex can comprise, consist essentially of, or consist of a chromium(II) halide, a chromium(II) carboxylate, or a chromium(II) β-diketonate, or alternatively a chromium(III) halide, a chromium(III) carboxylate, or a chromium(III) β-diketonate. In other non-limiting embodiments, the chromium compound and / or the chromium compound of the heteroatom-ligand chromium compound complex can comprise, consist essentially of, or consist of a chromium(II) halide, alternatively a chromium(III) halide, alternatively a chromium(II) carboxylate, alternatively a chromium(III) carboxylate, alternatively a chromium(II) β-diketonate, or alternatively a chromium(III) β-diketonate. The halides, carboxylates, and β-diketonates are described independently herein, and these halides, carboxylates, and β-diketonates, and these independently described halides, carboxylates, and β-diketonates, may be utilized without limitation and in any combination to further describe the chromium compounds and / or chromium compounds of the heteroatom-ligand chromium compound complexes.In a further non-limiting embodiment, the chromium compound and / or the chromium compound of the heteroatom-ligand chromium compound complex can be chromium(II) chloride, chromium(III) chloride, chromium(II) fluoride, chromium(III) fluoride, chromium(II) bromide, chromium(III) bromide, chromium(II) iodide, chromium(III) iodide, chromium(II) acetate, chromium(III) acetate, chromium(II) 2-ethylhexanoate, chromium(III) 2-ethylhexanoate, chromium(II) triflate, chromium(III) triflate, chromium(II) nitrate, chromium(III) nitrate, chromium(II) acetylacetonate, chromium(III) acetylacetonate, chromium(II) hexafluoroacetylacetonate, chromium(III) hexafluoroacetylacetonate, chromium(III) Alternatively, the composition may comprise, consist essentially of, or consist of chromium(III) benzoylacetonate, or chromium(III) benzoylacetonate, alternatively chromium(III) chloride, chromium(III) fluoride, chromium(III) bromide, chromium(III) iodide, chromium(III) chloride (THF) complex, chromium(III) acetate, chromium(III) 2-ethylhexanoate, chromium(III) triflate, chromium(III) nitrate, chromium(III) acetylacetonate, chromium(III) hexafluoroacetylacetonate, or chromium(III) benzoylacetonate, alternatively chromium(III) chloride, or chromium(III) acetylacetonate, alternatively chromium(III) chloride, or alternatively chromium(III) acetylacetonate.

[0179] In a non-limiting embodiment, one or more first training heteroatom ligand-metal compound complexes, each comprising a first training heteroatom ligand, can have, among other things, i) the structure NPFCr1, where R 1 is 2,6-dimethylphenyl, and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 is 2,6-dimethylphenyl, and R 3 is H and R 4 and R 5is phenyl and X is chlorine; R 1 is 2,6-dimethylphenyl, and R 3 is H and R 4 and R 5 is 4-methoxyphenyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 3 is H and R 4 and R 5 is phenyl and X is chlorine; and R 1 is 2,4,6-trimethylphenyl, and R 3 is H and R 4 and R 5 is 4-methoxyphenyl and X is chlorine), ii) structure NPACr1 (wherein R 1 is 2,6-dimethylphenyl, and R 2 is phenyl and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is phenyl and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 is 2,6-dimethylphenyl, and R 2 is phenyl and R 3 is H and R 4 and R 5 is phenyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is phenyl and R 3 is H and R 4 and R 5 is phenyl and X is chlorine; R 1is 2,6-dimethylphenyl, and R 2 is 4-methylbenzyl, and R 3 is H and R 4 and R 5 is phenyl and X is chlorine; R 1 is 2,6-dimethylphenyl, and R 2 is phenyl and R 3 is H and R 4 and R 5 is 4-methoxyphenyl and X is chlorine; R 1 is 2,6-dimethylphenyl, and R 2 is 4-t-butylphenyl, and R 3 is H and R 4 and R 5 is methyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is 4-t-butylphenyl, and R 3 is H and R 4 and R 5 is methyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is 4-methylbenzyl, and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is 4-methylbenzyl, and R 3 is H and R 4 and R 5 is phenyl and X is chlorine; R 1 is 3,5-dimethylphenyl, and R 2 is phenyl and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is 4-methylbenzyl, and R 3 is H and R4 and R 5 is 4-methoxyphenyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is 4-methylbenzyl, and R 3 is H and R 4 is t-butyl, and R 5 is phenyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is 4-methylbenzyl, and R 3 is H and R 4 is methyl and R 5 is phenyl and X is chlorine; R 1 and R 2 are linked to form a prop-1,3-ylene group, and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 and R 2 are linked to form a but-1,4-ylene group, and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is 4-methylbenzyl, and R 3 is H and R 4 and R 5 are linked to form a buta-1,4-ylene group, and X is chlorine; R 1 is 2,4,6-trimethylphenyl, and R 2 is 4-methylbenzyl, and R 3 is H and R 4 and R 5 are linked to form a 2,2'-dimethylbiphenylene group, and X is chlorine; iii) structure GUCr1, where R 1 is 2-methylphenyl, and R 2a is 2-methylphenyl, and R 2b is H and R 3 is H and R4 and R 5 is isopropyl and X is chlorine; R 1 is 2,6-dimethylphenyl, and R 2a is phenyl and R 2b is H and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine; R 1 is 2,6-dimethylphenyl, and R 2a is phenyl and R 2b is H and R 3 is H and R 4 and R 5 is phenyl and X is chlorine; R 1 is 2,6-dimethylphenyl, and R 2a and R 2b is phenyl and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine), iv) structure GUCr4 (wherein L 12 is prop-1,3-ylene, and L 23 is propa-1,3-ylene, and R 4 and R 5 is isopropyl and X is chlorine; L 12 is prop-1,3-ylene, and L 23 is propa-1,3-ylene, and R 4 and R 5 is cyclopentyl and X is chlorine; L 12 is prop-1,3-ylene, and L 23 is propa-1,3-ylene, and R 4 and R 5 is cyclohexyl and X is chlorine; L 12 is prop-1,3-ylene, and L 23 is propa-1,3-ylene, and R 4 and R 5 is phenyl and X is chlorine; L 12 is buta-1,3-ylene, and L 23is propa-1,3-ylene, and R 4 and R 5 is isopropyl and X is chlorine; L 12 is buta-1,3-ylene, and L 23 is propa-1,3-ylene, and R 4 and R 5 is cyclopentyl and X is chlorine; L 12 is buta-1,3-ylene, and L 23 is buta-1,3-ylene, and R 4 and R 5 is isopropyl and X is chlorine; L 12 is buta-1,3-ylene, and L 23 is buta-1,3-ylene, and R 4 and R 5 is phenyl and X is chlorine; L 12 is ethene-1,2-ylene, and L 23 is propa-1,3-ylene, and R 4 and R 5 is isopropyl and X is chlorine; L 12 is ethene-1,2-ylene, and L 23 is propa-1,3-ylene, and R 4 and R 5 is cyclopentyl and X is chlorine; L 12 is ethene-1,2-ylene, and L 23 is propa-1,3-ylene, and R 4 and R 5 is cyclohexyl and X is chlorine; L 12 is phen-1,2-ylene, and L 23 is eth-1,2-ylene, and R 4 and R 5 is isopropyl and X is chlorine), and v) structure HCPACr2 (where T is sulfur, L 12 is ethene-1,2-ylene, and R 3 is H and R 4 and R 5 is isopropyl, X is chlorine; and T is sulfur, L12 is phen-1,2-ylene, and R 3 is H and R 4 and R 5 is isopropyl and X is chlorine.

[0180] In non-limiting embodiments, the one or more first training heteroatom ligands associated with the one or more first training heteroatom ligand-metal compound complexes can be selected from any one or more of HL1, HL2, HL3, HL4, HL5, HL6, HL7, HL7, and HL9, among others. In some non-limiting embodiments, the one or more first training heteroatom ligand-metal compound complexes can be selected from diphosphinoamine chromium compound complexes, which can be any one or more of chromium compound complexes among others: HLCr1, HLCr2, HLCr3, HLCr4, HLCr5, HLCr6, HLCr7, HLCr8, and HLCr9. In other non-limiting embodiments, the one or more first training heteroatom ligand-metal compound complexes can be selected from diphosphinoamine chromium compound complexes, which can be any one or more of chromium(III) chloride or chromium(III) acetylacetonate complexes of HLCr1, HLCr2, HLCr3, HLCr4, HLCr5, HLCr6, HLCr7, HLCr8, and HLCr9, among others. [ka]

[0181] Although not shown in the names and formulas of all chromium compounds and / or the formulas and structures of heteroatom-ligand chromium compound complexes provided herein, those skilled in the art will recognize the neutral ligand Q (which can be represented by the general heteroatom ligand formula [(HetLig)CrX q L r ] 3-qIt will be appreciated that L) in (A) may refer to chromium compounds and / or heteroatom-ligand chromium compound complexes described / illustrated herein that do not explicitly disclose / show a neutral ligand. Furthermore, while some of the chromium compounds and / or heteroatom-ligand chromium compound complexes described / illustrated / provided herein do not formally indicate the presence of a neutral ligand, it will be understood that chromium compounds and / or heteroatom-ligand chromium compound complexes having neural ligands (e.g., nitriles and ethers, among others) are implicitly and fully contemplated as potential chromium compounds and / or heteroatom-ligand chromium compound complexes that may be utilized in the catalyst systems used in the inventive embodiments described herein.

[0182] Generally, when present, the neutral ligands of any chromium compound and / or heteroatomic ligand chromium compound complex can independently be any neutral ligand that forms an isolable compound with the chromium compound and / or heteroatomic ligand chromium compound complex. In some embodiments, each neutral ligand can independently be a nitrile or an ether, alternatively a nitrile, or alternatively an ether. The number of neutral ligands, q (as represented by the general formula [(HetLig)CrX q L r ] 3-q The r) in (A) can be any number that forms an isolatable compound with the chromium compound and / or heteroatom ligand chromium compound complex. In some embodiments, the number of neutral ligands can be 0-6, alternatively 0-3, alternatively 0, alternatively 1, alternatively 2, alternatively 3, or alternatively 4.

[0183] Generally, each nitrile ligand independently has a C2-C 20 Nitriles, or alternatively C2-C 10 In some embodiments, each nitrile ligand is independently a C2-C 20 Aliphatic nitriles, C7-C 20 Aromatic nitriles, C8-C 20 Aralkanenitrile, or any combination thereof, alternatively C2-C 20 Aliphatic nitriles, alternatively C7-C20 Aromatic nitriles, or alternatively C8-C 20 In some embodiments, each nitrile ligand can be independently a C2-C 10 Aliphatic nitriles, C7-C 10 Aromatic nitriles, C8-C 10 Aralkanenitrile, or any combination thereof, alternatively C1-C 10 Aliphatic nitriles, alternatively C7-C 10 Aromatic nitriles, or alternatively C8-C 10 In an embodiment, each aliphatic nitrile can independently be acetonitrile, propionitrile, butyronitrile, benzonitrile, or any combination thereof; alternatively, acetonitrile, alternatively, propionitrile, alternatively, butyronitrile, or alternatively, benzonitrile.

[0184] Generally, each ether ligand independently has a C2-C 40 Ether, alternatively C2 to C 30 Ether, or alternatively C2 to C 20 In some embodiments, each ether ligand is independently a C2-C 40 Aliphatic ethers, C3-C 40 Aliphatic cyclic ethers, C4-C 40 Aromatic ethers, alternatively C2-C 40 Aliphatic acyclic ether or C3-C 40 Aliphatic cyclic ethers, alternatively C2-C 40 Aliphatic acyclic ethers, alternatively C3-C 40 Aliphatic cyclic ethers, or alternatively C4-C 40 In some embodiments, each ether ligand is independently a C2-C 30 Aliphatic ethers, C3-C 30 Aliphatic cyclic ethers, C4-C 30 Aromatic ethers, alternatively C2-C 30 Aliphatic acyclic ether or C3-C 30 Aliphatic cyclic ethers, alternatively C2-C 30Aliphatic acyclic ethers, alternatively C3-C 30 Aliphatic cyclic ethers, or alternatively C4-C 30 In another embodiment, each ether ligand is independently a C2-C 20 Aliphatic ethers, C3-C 20 Aliphatic cyclic ethers, C4-C 20 Aromatic ethers, alternatively C2-C 20 Aliphatic acyclic ether or C3-C 20 Aliphatic cyclic ethers, alternatively C2-C 20 Aliphatic acyclic ethers, alternatively C3-C 20 Aliphatic cyclic ethers, or alternatively C4-C 20In some embodiments, each ether ligand is independently selected from dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, tetrahydrofuran, dihydrofuran, 1,3-dioxolane, tetrahydropyran, dihydropyran, pyran, dioxane, furan, benzofuran, isobenzofuran, dibenzofuran, diphenyl ether, ditolyl ether, or any combination thereof, alternatively dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methyl propyl ether, methyl butyl ether, or any combination thereof; tetrahydrofuran, dihydrofuran, 1,3-dioxolane, tetrahydropyran, dihydropyran, pyran, dioxane, or any combination thereof. It may be any combination of: furan, benzofuran, isobenzofuran, dibenzofuran, or any combination thereof; diphenyl ether, ditolyl ether, or any combination thereof, alternatively dimethyl ether, alternatively diethyl ether, alternatively dipropyl ether, alternatively dibutyl ether, alternatively methyl ethyl ether, alternatively methyl propyl ether, alternatively methyl butyl ether, alternatively tetrahydrofuran, alternatively dihydrofuran, alternatively 1,3-dioxolane, alternatively tetrahydropyran, alternatively dihydropyran, alternatively pyran, alternatively dioxane, alternatively furan, alternatively benzofuran, alternatively isobenzofuran, alternatively dibenzofuran, alternatively diphenyl ether, or alternatively ditolyl ether.

[0185] Thus, in any of the one or more ground state model structures and any of the plurality of transition state model structures, the model structure may be: [ka] and heteroatom ligands which may be independently selected from: R 1is hydrogen or C1-C 20 may be an organyl group, R 2 However, C1~C 20 may be an organyl group, T can be oxygen or sulfur; R 2a and R 2b are independent, C1~C 20 may be an organyl group, L 12 and L 23 are independent, C2~C 20 may be an organylene group, L 22 But C3~C 20 may be an organylene group, R 3 is hydrogen or C1-C 20 may be an organyl group, R 4 and R 5 are independently hydrogen or C1-C 20 may be an organyl group, R 1 and R 2 optionally combined to form L 12r and L 12r But C3~C 30 is an organylene group, R 4 and R 5 optionally combined to form L 45 and L 45 But C4~C 30 It is an organylene group.

[0186] In a further aspect, the model structure may include a heteroatom ligand, which may be independently selected from NPF-1, NPA-1, Gu-1, Gu-2, Gu-3, Gu-4, Gu-5, or HCPA-1 presented herein, wherein: R 1 But hydrogen, C1~C 20 Hydrocarbyl groups, or C1-C 20 may be a heterohydrocarbyl group, R 2 However, C1~C 20Hydrocarbyl group or C1-C 20 may be a heterohydrocarbyl group, R 2a and R 2b are independent, C1~C 20 Hydrocarbyl group or C1-C 20 heterohydrocarbyl groups, L 12 and L 23 are independent, C2~C 20 Hydrocarbylene group or C2-C 20 heterohydrocarbylene groups, L 22 But C3~C 20 Hydrocarbylene group or C3-C 20 may be a heterohydrocarbylene group, R 3 But hydrogen, C1~C 20 Hydrocarbyl groups, or C1-C 20 may be a heterohydrocarbyl group, R 4 and R 5 are independent, C1~C 20 Hydrocarbyl group or C1-C 20 heterohydrocarbyl groups, R 1 and R 2 optionally combined to form L 12r and L 12r But C3~C 20 Hydrocarbylene group or C3-C 20 may be a heterohydrocarbylene group, R 4 and R 5 optionally combined to form L 45 and L 45 But C4~C 20 Hydrocarbylene group or C4-C 20 It may be a heterohydrocarbylene group.

[0187] Additional aspects of the model structures may be found in the R 1 described independently herein for NPF-1, NPA-1, Gu-1, Gu-2, Gu-3, Gu-4, Gu-5, or HCPA-1 presented herein. 1 , R 2 , T, R 2a , R 2b , R 3 , R 4 , R 5 , L 12 , L 22 , L 23 The various "R" and "L" moieties in NPF-1, NPA-1, Gu-1, Gu-2, Gu-3, Gu-4, Gu-5, or HCPA-1, where "hydrocarbyl," "hydrocarbylene," "heterohydrocarbyl," or "heterohydrocarbylene" moieties are listed, are encompassed by reference to the definitions section where these terms are defined. For example, the term "hydrocarbyl" or "hydrocarbylene" encompasses aryl and arylene; alkyl and alkanediyl (or "alkylene"); cycloalkyl and cycloalkanediyl (or "cycloalkylene"); aralkyl and aralkanediyl (or "aralkylene"), respectively, where the specified number of carbon atoms is appropriate for the selected group. Similarly, the definitions section describes moieties that may be encompassed by the term "hydrocarbyl" or "hydrocarbylene."

[0188] In a further aspect, in any of the one or more ground state model structures and any of the plurality of transition state model structures, the model structures include: [ka] and heteroatom ligands which may also be independently selected from During the ceremony, Each R 1s , R 2s , R 5s , R 11s , R 12s , R13s , and R 14s are independently hydrogen or C1-C 20 may be selected from organyl groups, Each L 1s , L 3s , and L 4s are independent, C2~C 20 organylene groups, Any two geminal R 1s optionally combined to form L 11s and L 11s But C3~C 30 is an organylene group, Any two geminal R 2s optionally combined to form L 22s and L 22s But C3~C 30 is an organylene group, Any germinal R 11s and R 12s optionally combined to form L 12s and L 12s But C3~C 30 is an organylene group, Any germinal R 13s and R 14s optionally combined to form L 34s and L 34s But C3~C 30 It is an organylene group.

[0189] In a further aspect, the model structure may include a heteroatom ligand, which may be independently selected from NRN-1, PRP-1, SRS-1, PNP-1, NRNRN-1, PRPRP-1, SRSRS-1, PRNRP-1, or NRPRN-1 as presented above, wherein: Each R 1s , R 2s , R 5s , R 11s , R 12s , R 13s , and R 14s are independently hydrogen, C1 to C 20 Hydrocarbyl groups, or C1-C 20heterohydrocarbyl groups, Each L 1s , L 3s , and L 4s are independent, C2~C 20 Hydrocarbylene group or C2-C 20 heterohydrocarbylene groups, Any two geminal R 1s optionally combined to form L 11s and L 11s But C2~C 20 Hydrocarbylene group or C2-C 20 is a heterohydrocarbylene group, Any two geminal R 2s optionally combined to form L 22s and L 22s But C2~C 20 Hydrocarbylene group or C2-C 20 is a heterohydrocarbylene group, Any germinal R 11s and R 12s optionally combined to form L 12s and L 12s But C2~C 20 Hydrocarbylene group or C2-C 20 is a heterohydrocarbylene group, Any germinal R 13s and R 14s optionally combined to form L 34s and L 34s But C2~C 20 Hydrocarbylene group or C2-C 20 It is a heterohydrocarbylene group.

[0190] Additional aspects of the model structures may be found in the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 1s , R 2s , R 5s , R 11s , R12s , R 13s , R 14s , L 1s , L 3s , L 4s , L 11s , L 12s , L 22s , and L 34s The "hydrocarbyl," "hydrocarbylene," "heterohydrocarbyl," or "heterohydrocarbylene" moieties are recited in NRN-1, PRP-1, SRS-1, PNP-1, NRNRN-1, PRPRP-1, SRSRS-1, PRNRP-1, or NRPRN-1, and reference is also made to the definitions section where these terms are defined.

[0191] In general, the organoaluminum compound utilized in the catalyst systems disclosed herein can be any organoaluminum compound capable of catalyzing the formation of oligomeric products in conjunction with a heteroatom-ligand chromium compound complex (or a chromium compound and a heteroatom ligand). In some embodiments, the organoaluminum compound can be an aluminoxane, an alkylaluminum compound, or any combination thereof; alternatively, an aluminoxane, or alternatively, an alkylaluminum compound. In some embodiments, the alkylaluminum compound can be a trialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide, or any combination thereof. In some embodiments, the alkylaluminum compound can be a trialkylaluminum, an alkylaluminum halide, or any combination thereof; alternatively, a trialkylaluminum, an alkylaluminum alkoxide, or any combination thereof; or alternatively, a trialkylaluminum. In other embodiments, the alkylaluminum compound can be a trialkylaluminum, alternatively, an alkylaluminum halide, or alternatively, an alkylaluminum alkoxide. In certain embodiments, the aluminoxane utilized in the catalyst systems utilized in the processes and systems can be any aluminoxane capable of catalyzing the formation of oligomeric products in conjunction with a heteroatom-ligand chromium compound complex (or a chromium compound and a heteroatom ligand). In a non-limiting embodiment, the aluminoxane has Formula I: [ka] where R' is a linear or branched alkyl group. The alkyl groups of the aluminoxanes and alkylaluminum compounds are described independently herein and may be utilized without limitation to further describe the aluminoxanes and / or alkylaluminum compounds having Formula I. Generally, n in Formula I can be greater than 1, or alternatively greater than 2. In some embodiments, n can range from 2 to 15, or alternatively, from 3 to 10.

[0192] In some aspects, each halide of any alkylaluminum halide disclosed herein can independently be a fluoride, chloride, bromide, or iodide, or alternatively a chloride, bromide, or iodide. In some embodiments, each halide of any alkylaluminum halide disclosed herein can be a fluoride, alternatively a chloride, alternatively a bromide, or alternatively an iodide.

[0193] In one embodiment, each alkyl group of the aluminoxane and / or alkylaluminum compound is independently C1 to C 20 Alkyl groups, alternatively C1-C 10 The alkyl group of the aluminoxane and / or alkylaluminum compound may be an alkyl group, or alternatively a C1-C6 alkyl group. In certain embodiments, the alkyl groups of the aluminoxane and / or alkylaluminum compound may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, alternatively methyl, ethyl, butyl, hexyl, or octyl. In some embodiments, the alkyl groups of the aluminoxane and / or alkylaluminum compound may be methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, or n-octyl, alternatively methyl, ethyl, n-butyl, or isobutyl, alternatively methyl, alternatively ethyl, alternatively n-propyl, alternatively n-butyl, alternatively isobutyl, alternatively n-hexyl, or alternatively n-octyl.

[0194] In some embodiments, each alkoxide group in any alkylaluminum alkoxide disclosed herein is independently C1-C 20 Alkoxy groups, C1-C 10In some embodiments, each alkoxide group in any alkylaluminum alkoxide disclosed herein can independently be a methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy group, alternatively a methoxy, ethoxy, butoxy, hexoxy, or octoxy group. In some embodiments, each alkoxide group of any alkylaluminum alkoxide disclosed herein can independently be a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an iso-butoxy group, an n-hexoxy group, or an n-octoxy group; alternatively, a methoxy group, an ethoxy group, an n-butoxy group, or an iso-butoxy group; alternatively, a methoxy group, alternatively, an ethoxy group, alternatively, an n-propoxy group, alternatively, an n-butoxy group, alternatively, an iso-butoxy group, alternatively, an n-hexoxy group, or alternatively, an n-octoxy group.

[0195] In non-limiting aspects, useful trialkylaluminum compounds can include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or mixtures thereof. In some non-limiting embodiments, useful trialkylaluminum compounds can include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof. In other non-limiting embodiments, useful trialkylaluminum compounds can include trimethylaluminum, alternatively, triethylaluminum, alternatively, tripropylaluminum, alternatively, tri-n-butylaluminum, alternatively, tri-isobutylaluminum, alternatively, trihexylaluminum, or alternatively, tri-n-octylaluminum.

[0196] In non-limiting embodiments, useful alkylaluminum halides can include diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In some non-limiting embodiments, useful alkylaluminum halides can include diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In other non-limiting embodiments, useful alkylaluminum halides can include diethylaluminum chloride, alternatively diethylaluminum bromide, alternatively ethylaluminum dichloride, or alternatively ethylaluminum sesquichloride.

[0197] In non-limiting embodiments, the aluminoxane can comprise or consist essentially of methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, t-butylaluminoxane, 1-pentylaluminoxane, 2-ethylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or mixtures thereof. In some non-limiting embodiments, the aluminoxane can comprise or consist essentially of methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, t-butylaluminoxane, or mixtures thereof. In other non-limiting embodiments, the aluminoxane can comprise or consist essentially of methylaluminoxane (MAO), alternatively ethylaluminoxane, alternatively modified methylaluminoxane (MMAO), alternatively n-propylaluminoxane, alternatively iso-propyl-aluminoxane, alternatively n-butylaluminoxane, alternatively sec-butylaluminoxane, alternatively iso-butylaluminoxane, alternatively t-butylaluminoxane, alternatively 1-pentyl-aluminoxane, alternatively 2-pentylaluminoxane, alternatively 3-pentyl-aluminoxane, alternatively iso-pentyl-aluminoxane, or alternatively neopentylaluminoxane.

[0198] Input variables for the model ground state structure and model transition state structure In certain embodiments, in the disclosed methods, any of the one or more training heteroatom ligand-metal compound complexes and any of the one or more target heteroatom ligand-metal compound complexes are [(HetLig)CrX q L r ] 3-q (A) may have a formula independently selected from: HetLig represents the one or more first training heteroatom ligands; X is an anionic ligand and q is an integer; L is a neutral ligand and r is an integer; any two or more of the X and L ligands may be linked to form a multidentate ligand; Each of the selected n input variables I 1 , I 2 , …I n has one or more ground state model structures GS of formula (A) A1 , …GS Ap or a plurality of transition state model structures TS associated with one or more ground state model structures. A1 , T.S. A2 , …TS Am The structural or electronic properties of any of

[0199] The input variables will vary based on the type of heteroatom ligand and the specific heteroatom ligand coordinated to chromium in the ground state model structure and the transition state model structure in the training heteroatom ligand-metal compound complex. In one aspect, when the model structure includes a heteroatom ligand selected from the general structures NPF-1, NPA-1, Gu-1, Gu-2, Gu-3, Gu-4, Gu-5, or HCPA-1 presented herein, the chromium heteroatom ligand moiety independently has the following structure: [ka] may be selected from In the structure, R 1 , R 2 , T, R 2a , R 2b , L 12 , L 23 , L 22 , R 3 , R 4 , R 5 L 12r , and L 45 is defined as presented herein, and " *" represents any additional bond required in [1] any one or more ground state model structures or any one of multiple transition state model structures derived from one or more first training heteroatom ligand-metal compound complexes; [2] any one or more ground state model structures or any one of multiple transition state model structures derived from one or more first target heteroatom ligand-metal compound complexes; or [3] any of the heteroatom ligand-metal complexes, the first training heteroatom ligand-metal compound complexes, and / or the first target heteroatom ligand-metal compound complexes.

[0200] In one embodiment, given a model structure including the chromium heteroatom ligand moiety NPFCrM-1, NPACrM-1, GuCrM-1, GuCrM-2, GuCrM-3, GuCrM-4, GuCrM-5, or HCPACrM-1, n input variables I 1 , I 2 , …I n The following variables: (a) Cr-P distance (Å), (b) Cr-N distance (Å), (c) Cr---R distance on α-C (Å), (d) P-Cr-N angle (degrees), (e) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to or within bonding distance of the Cr atom; (f) Cr-NC angle (degrees), (g) distance from the pocket (Å); (h)Cr---α-C distance (Å), (i)Cr CHELPG (atomic charge), (j)P CHELPG(atomic charge), (k)N CHELPG (atomic charge), (l) Cr-NCN dihedral angle (degrees), (m)Cr-PNC dihedral angle (degrees), (n)P-Cr-NC dihedral angle (degrees), (o)PNCN dihedral angle (degrees), (p) CCNC dihedral angle (degrees), or (q) percent buried volume, may include or be selected from any one or more of:

[0201] Figures 1, 2A, 2B, and 2C illustrate some of the input variables listed above using the transition states of exemplary heteroatomic ligand-chromium compound complexes. With reference to these figures, Cr-R is the distance from Cr to the group on the carbon alpha to the nitrogen bonded to Cr in the structure of Figure 1. The Cr-α-C distance is the linear distance to the carbon itself, alpha to the nitrogen in the structure of Figure 1, to which the R group is bonded. With reference to Figure 1, the C-Cr-N angle is the angle formed by the chromium atom and the carbon atom bonded to the substrate (i.e., the carbon atom resulting from ethylene growth in the ground state and / or transition state), the Cr atom, and the nitrogen atom of the heteroatomic ligand complexed with the chromium atom in the ground and transition states, as applicable. Those skilled in the art will be able to use Figures 1, 2A, 2B, and 2C to calculate the n corresponding input variables I for the heteroatom ligand-chromium compound complexes, ground states of heteroatom ligand-chromium compound complexes, transition states of heteroatom ligand-chromium compound complexes, and chromium heteroatom ligand moieties NPFCrM-1, NPACrM-1, GuCrM-1, GuCrM-2, GuCrM-3, GuCrM-4, GuCrM-5, or HCPACrM-1 described herein. 1 , I 2 , …I n It will be possible to determine.

[0202] 2A-2C provide further explanation and definitions for some of these input variables. For example, these figures illustrate descriptors that may be extracted for machine learning analysis, including descriptions of geometric and electrostatic charge input variables in FIG. 2A, a definition of percent buried volume in FIG. 2B, and a definition of distance from pocket in FIG. 2C. As illustrated, "distance from pocket" is defined as follows: distance from pocket (d) = R(Cr-N1) sin(∠Cr-N1-P). That is, distance from pocket is the sine of the Cr-N1 distance × Cr-N1-P angle, which describes how far the Cr metal is located from the (P,N) ligand. The buried volume percent is defined as the extent to which the first coordination sphere of the Cr metal center is occupied by (P,N) ligands, as used in Falivene, L., Cao, Z., Petta, A., Serra, L., Poater, A., Oliva, R., Scarano, V., Cavallo, L. Towards the Online Computer-Aided Design of Catalytic Pockets. Nat. Chem. 2019, 11(10), 872-879 (https: / / doi.org / 10.1038 / s41557-019-0319-5).

[0203] In a further aspect, when the model structure includes a heteroatom ligand selected from the general structures NRN-1, PRP-1, SRS-1, PNP-1, NRNRN-1, PRPRP-1, SRSRS-1, PRNRP-1, or NRPRN-1 presented herein, the chromium heteroatom ligand moiety can independently have the following structure: [ka] may be selected from In the structure, R 1s , R 2s , R 5s , R 11s , R 12s , R 13s , R 14s , L 1s , L 3s , L4s , L 11s , L 22s , L 12sr , and L 34s is defined as presented herein, and " * " represents any additional bond required in [1] any one or more ground state model structures or any one of multiple transition state model structures derived from one or more first training heteroatom ligand-metal compound complexes; [2] any one or more ground state model structures or any one of multiple transition state model structures derived from one or more first target heteroatom ligand-metal compound complexes; or [3] any of the heteroatom ligand-metal complexes, the first training heteroatom ligand-metal compound complexes, and / or the first target heteroatom ligand-metal compound complexes.

[0204] In one embodiment, given a model structure comprising the chromium heteroatom ligand moiety NRNCrM-1, PRPCrM-1, SRSCrM-1, PNPCrM-1, NRNRNCrM-1, PRPRPCrM-1, SRNRSCrM-1, PRNRPCCrM-1, or NRPRNCrM-1, n input variables I 1 , I 2 , …I n The following variables: (a) First, second, or third Cr-N distance (Å), (b) the first, second, or third Cr-P distance (Å); (c) First or second Cr-S distance (Å), (d) any one or more N-Cr-N angles (degrees); (e) any one or more P-Cr-P angles (degrees); (f) any one or more S-Cr-S angles (degrees); (g) any one or more S-Cr-N angles (degrees); (h) any one or more N-Cr-P angles (degrees); (i) the C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to or within bonding distance of the Cr atom; (j) C-Cr-P angle (degrees), (k)C-Cr-S angle (degrees), (l) Cr-NC angle (degrees), (m)Cr-PC angle (degrees), (n)Cr-SC angle (degrees), (o) Cr-PC angle (degrees), (p) Cr---R distance on α-C (Å), (q) distance from the pocket (Å); (r)Cr---α-C, (s)Cr CHELPG (atomic charge), (t) Any P CHELPG (atomic charge), (u) any N CHELPG (atomic charges), (v) any chelate Cr-NCC dihedral angle (degrees); (w) any chelate Cr-PCC dihedral angle (degrees); (x) any chelate Cr-SCC dihedral angle (degrees), or (y) percent buried volume; may include or be selected from any one or more of:

[0205] FIG. 2B illustrates the definition of percent buried volume, and FIG. 2C illustrates the definition of distance from pocket.

[0206] Performance parameters and adjustment of input variables to approximate corresponding output variables In the method of the present disclosure, a first target heteroatom ligand-metal compound complex for olefin oligomerization is prepared by incorporating one or more n input variables I identified from a machine learning model. 1 , I 2 , …I n The first target heteroatom ligand-metal compound complexes are generated based on one or more ground state model structures GS B1 , …GS Bx(x is an integer), or a plurality of transition state model structures TS associated with one or more ground state model structures. B1 , T.S. B2 , …TS By n output variables O having quantitative values ​​corresponding to any of the structural or electronic properties of 1 , O 2 , …O n The first target heteroatom ligand-metal compound complex comprises a first target heteroatom ligand generated by computationally evaluating a first training model against a machine learning model to discover desired adjustments that will generate the first target heteroatom ligand.

[0207] In some embodiments, one or more performance parameters associated with olefin oligomerization reactions are identified, and the values ​​of the performance parameters for one or more first training heteroatom ligand-metal compound complexes and a first target heteroatom ligand-metal compound complex are computationally evaluated in light of the training compounds, experimentally validated, and subjected to further testing and redesign. In this manner, catalyst performance can be predicted and improved.

[0208] As disclosed herein, one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes. A1 , …GS Ap Each of the transition state model structures TS A1 , T.S. A2 , …TS Am For each of the n input variables I 1 , I 2 , …I n The quantitative values ​​assigned to may be based on calculated, measured, or estimated values, or any combination thereof. A1 , …GS Ap Each of the transition state model structures TS A1 , T.S. A2 , …TS AmFor each of the n input variables I 1 , I 2 , …I n These quantitative values ​​assigned to can independently be raw or normalized values. Furthermore, the ground state model structure GS A1 , …GS Ap and the transition state model structure TS A1 , T.S. A2 , …TS Am In determining the relative energy of each of the above, these determined relative energies can be independently the relative energy of a possible ensemble of conformations of the ground state model structure and the transition state model structure or one specific conformation. Also, n input variables I associated with [1] ΔG(TS-GS) or ΔΔG(TS-GS) or [2] ΔG(TS-TS) or ΔΔG(TS-TS) 1 , I 2 , …I n In one or more of these ΔG or ΔΔG energy differences can be based on Boltzmann ensemble ΔG or ΔΔG values. For example, as described in detail in this disclosure, in one embodiment, a ground state model structure G S derived from one or more first training heteroatom ligand-metal compound complexes A1 , …GS Ap One or more of the transition state model structures TS A1 , T.S. A2 , …TS Am Any of the above may be calculated using density functional theory (DFT) calculations. Furthermore, generating the machine learning model of the disclosed method may include a Gaussian process algorithm or a random forest algorithm.

[0209] According to one aspect of the present disclosure, the one or more performance parameters associated with an olefin oligomerization reaction may be selected from (a) olefin oligomer purity (also referred to herein as purity or product purity), (b) olefin oligomer selectivity (also referred to herein as selectivity or product selectivity), (c) heteroatom ligand-metal compound complex productivity (also referred to herein as activity / productivity or oligomer productivity), or (d) any combination thereof. More specifically, in certain embodiments, the one or more performance parameters associated with an olefin oligomerization reaction may be selected from (a) 1-hexene purity, (b) 1-octene purity, (c) 1-hexene:1-octene ratio (C6 / C8 ratio), (d) 1-hexene productivity, (e) 1-octene productivity, (f) total productivity of 1-hexene and 1-octene, (g) trimerization selectivity to 1-hexene, (h) tetramerization selectivity to 1-octene, (i) 1-octene efficiency of the fourth ethylene addition, or any combination thereof. Based on these performance parameters, relevant ground state model structures and relevant transition state model structures may include or be selected as follows:

[0210] With respect to olefin productivity, the performance parameter associated with the olefin oligomerization reaction may be the 1-hexene productivity, the 1-octene productivity, or the total productivity of 1-hexene and 1-octene of the heteroatom ligand-metal compound complex. Thus, if the performance parameter is one of these productivity parameters, [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes. A1 , …GS Ap GS I -I, G.S. I -II, GS I -III, GS I -IV, GS I -V, GS I -VI, GS I-VII, or any combination thereof, and may be independently selected therefrom; [2] a plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; A1 , T.S. A2 , …TS Am TS I -I, T.S. I -II, TS I -III, TS I -IV, TS I -V, or any combination thereof, and may be independently selected therefrom; [3] one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; B1 , …GS Bp GS T -I, G.S. T -II, GS T -III, GS T -IV, GS T -V, GS T -VI, GS T -VII, or any combination thereof, and / or [4] a plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 , T.S. B2 , …TS Bm TS T -I, T.S. T -II, TS T -III, TS T -IV, TS T -V, or any combination thereof. When the one or more performance parameters related to the oligomerization of olefins includes or is selected from the productivity of the heteroatom ligand-metal compound complex, it can be determined based on grams of olefin oligomer(s) (grams of 1-hexene, grams of 1-octene, or total grams of 1-hexene and 1-octene) per gram of heteroatom ligand-metal compound complex per hour.

[0211] In one embodiment, for example, Figure 3 illustrates a 1-hexene turnover frequency reaction scheme that can be utilized to calculate / determine / estimate 1-hexene productivity, showing various ground and transition states and illustrating the energy barriers of the transition states that can contribute to the 1-hexene turnover frequency. The 1-hexene turnover frequency is then converted to 1-hexene productivity. In a further embodiment, the 1-octene turnover frequency can be calculated / determined / estimated using the ground and transition states illustrated in Figure 4 in addition to the ground and transition states of Figure 3. Figure 4 illustrates the 1-octene turnover frequency reaction scheme, along with its ground and transition states that must be included with the ground and transition states of Figure 3, starting from GS-VI. Thus, Figure 4, in addition to Figure 3, illustrates the energy barriers of all transition states that contribute to the 1-octene turnover frequency, which can then be converted to 1-octene productivity.

[0212] When determining the 1-octene turnover frequency in addition to the 1-hexene turnover frequency (and thus the combined turnover frequency), the 1-hexene turnover frequency and the 1-octene turnover frequency can be determined separately using the procedures given as examples herein for determining the 1-hexene turnover frequency, and then the separately determined turnover frequencies can be added to obtain the combined turnover frequency (the total turnover frequency of 1-hexene and 1-octene), which can then be converted to the productivity of 1-octene in addition to 1-hexene.

[0213] Regarding olefin selectivity, if the performance parameter relevant to an olefin oligomerization reaction is product selectivity (which may also be simply referred to as the C6 / C8 ratio or the C8 / C6 ratio), then Figure 5A illustrates the pathways by which 1-hexene and 1-octene may be formed. The ground state and transition state designations correspond to the ground state and transition state structures disclosed herein. As illustrated, the formation of both 1-hexene and 1-octene may proceed through a common ground state, GS-VI. Olefin selectivity is then determined by whether GS-VI undergoes β-hydrogen elimination and reductive elimination through TS-III to produce 1-hexene, or, alternatively, ethylene insertion into GS-VI leads to ground state GS-V, which then passes through TS-IV to produce the metallacyclanonane GS-VII, which then undergoes β-hydrogen elimination and reductive elimination to produce 1-octene. Using the rate-determining transition states (usually TS-III and TS-IV), product selectivity can then be determined using the relative amount of ground state GS-VI, which undergoes β-hydrogen elimination to give 1-hexene, versus the amount of ground state GS-VI, which inserts ethylene to give metallacyclononane GS-VII.

[0214] Thus, with respect to selectivity, if the performance parameter relevant to an olefin oligomerization reaction is 1-hexene selectivity or 1-octene selectivity (which may also be simply referred to as the C6 / C8 ratio), [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes. A1 , …GS Ap GS I [2] a plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; A1 , T.S. A2 , …TS Am TS I -III and TS I [3] one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex. B1 , …GSBp GS T -VI, and / or [4] a plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 , T.S. B2 , …TS Bm TS T -III and TS T -IV. Thus, when one or more performance parameters include or are selected from olefin oligomer selectivity, product selectivity can be determined by determining the Gibbs free energy difference between the transition state resulting from a common ground state (typically GS-VI) and 1) the transition state leading to 1-hexene production (typically TS-III) and 2) the transition state leading to 1-octene production (typically TS-IV). This Gibbs free energy difference can then be used to determine the amounts of 1-hexene and 1-octene from a plot of the calculated Gibbs free energy difference ΔΔG[TS(1-hexene)-TS(1-octene)] versus the experimentally determined Gibbs free energy difference of 1-hexene and 1-octene and the natural logarithm of a set of heteroatom ligand-metal compound complexes whose experimentally determined masses are known. Alternatively, the experimentally determined masses of 1-hexene and 1-octene can be replaced with calculated activities / productivities as calculated / determined / estimated by the methods described herein (via determination of turnover frequencies for 1-hexene and 1-octene production).

[0215] The selective oligomerization of ethylene to 1-hexene and 1-octene can produce by-products. As a result, the selectivity of the trimerization catalytic cycle to 1-hexene (also referred to as trimerization cycle selectivity to 1-hexene) and / or the selectivity of the tetramerization catalytic cycle to 1-octene (also referred to as tetramerization cycle selectivity to 1-octene) can be performance parameters related to olefin oligomerization influenced by the heteroatom ligand-metal compound complex. The trimerization cycle selectivity to 1-hexene is the number of moles of 1-hexene produced by the trimerization catalytic cycle divided by the number of moles of 1-hexene produced plus the number of moles of non-1-hexene by-products produced. The tetramerization cycle selectivity to 1-octene is the number of moles of 1-octene produced by the tetramerization catalytic cycle divided by the number of moles of 1-octene produced plus the number of moles of non-1-octene by-products produced.

[0216] Trimerization cycle selectivity to 1-hexene and tetramerization cycle selectivity to 1-octene can also be used to focus on specific non-1-hexene by-products produced by the trimerization catalytic cycle and / or specific non-1-octene by-products produced by the tetramerization catalytic cycle. In these cases, trimerization cycle selectivity is the moles of 1-hexene produced in the trimerization catalytic cycle divided by the moles of 1-hexene plus the specific non-1-hexene by-product produced, while tetramerization cycle selectivity to 1-octene is the moles of 1-octene produced in the tetramerization catalytic cycle compared to the total moles of 1-octene produced plus the specific non-1-octene by-product produced.

[0217] A specific set of non-1-hexene by-products produced by the trimerization catalytic cycle and / or non-1-octene by-products produced by the tetramerization catalytic cycle can arise when the 1-hexene or 1-octene produced in the trimerization and / or tetramerization replaces one of the ethylenes in the trimerization and / or tetramerization catalytic cycle. A particularly relevant example occurs when the produced 1-hexene or 1-octene is complexed with a chromium species to form a ground-state structure similar to GS-II of the trimerization and tetramerization catalytic cycles illustrated in Figure 5A. The 1-hexene or 1-octene involved in the trimerization and / or tetramerization cycle can adopt two different orientations, leading to two structurally distinct chromatocyclopentanes. 5B and 5C show how 1-hexene or 1-octene can propagate through a trimerization and / or tetramerization catalytic cycle to produce branched decene, branched dodecene, and / or branched tetradecene.

[0218] Furthermore, each different 1-hexene or 1-octene orientation leading to two structurally different substituted chromate cyclopentanes in turn leads to two different branched decenes (in the case of 1-hexene insertion) and two different branched dodecenes (in the case of 1-octene insertion) in the trimerization catalytic cycle and / or two different branched dodecenes (in the case of 1-hexene insertion) and two different branched tetradecenes (in the case of 1-octene insertion) in the tetramerization catalytic cycle.

[0219] The methods disclosed herein can be utilized to design / identify heteroatom ligand-metal compound complexes for the oligomerization of olefins that have a desired trimerization cycle selectivity to 1-hexene (based on all non-1-hexene catalyzed trimerization by-products or based on specific / specific non-1-hexene catalyzed trimerization by-products) and / or a desired tetramerization cycle selectivity to 1-octene (based on all non-1-octene hexene catalyzed trimerization by-products or based on specific / specific non-1-hexene catalyzed trimerization by-products).

[0220] Trimerization cycle selectivity to 1-hexene (either based on all non-1-hexene catalyzed trimerization by-products or based on specific / specific non-1-hexene catalyzed trimerization by-products) can be determined using different methods described herein.

[0221] In a first, non-limiting method, the amounts of 1-hexene and non-1-hexene-catalyzed trimerization by-products can be determined from the ratio of non-1-hexene-catalyzed trimerization by-products to 1-hexene. In this method, the ratio of non-1-hexene-catalyzed trimerization by-products to 1-hexene for each non-1-hexene-catalyzed trimerization by-product, which is the basis for trimerization cycle selectivity to 1-hexene, is determined by determining the Gibbs free energy difference, ΔΔG, between 1) the rate-limiting transition state / reaction step leading to 1-hexene production and 2) the rate-limiting transition state / reaction step leading to the non-1-hexene-catalyzed trimerization by-product. This Gibbs free energy difference can then be used to determine the amounts of 1-hexene and non-1-hexene-catalyzed trimerization by-products from a plot of the calculated Gibbs free energy difference, ΔΔG[TS(1-hexene)-TS(non-1-hexene-catalyzed trimerization by-products)], against the natural logarithm of the experimentally determined Gibbs free energy difference of 1-hexene and non-1-hexene-catalyzed trimerization by-products and a set of heteroatom ligand-metal compound complexes for which experimentally determined amounts are known. It should be noted that the transition states / reaction steps that determine the selectivity of a trimerization catalytic cycle are not predetermined but can only be determined by performing the necessary calculations on the trimerization catalytic cycle, and the specific transition states / reaction steps that determine selectivity may be ligand-dependent.

[0222] As an example, trimerization cycle selectivity to 1-hexene based on branched decenes and / or dodecenes can be calculated using the proposed trimerization reaction pathways illustrated in Figure 5A (via the GS-II / GS-III / GS-IV / GV-VI / TS-III ethylene trimerization pathway), Figure 5B (via the GS-IIa / GS-IIIa / GS-IVa / GV-VIa / TS-IIIa branched decene or dodecene pathway), and Figure 5C (via the GS-IIb / GS-IIIb / GS-IVb / GV-VIb / TS-IIIb branched decene or dodecene pathway). In this example, one would calculate 1) the Gibbs free energy of the rate-limiting transition state / reaction step for 1-hexene production as depicted in Figure 5A, 2) the Gibbs free energy of the rate-limiting step / reaction step for each branched decene and / or branched dodecene produced in the trimerization cycle as depicted in Figure 5B, and 3) the Gibbs free energy of the rate-limiting step / reaction step for each branched decene and / or branched dodecene produced in the trimerization cycle as depicted in Figure 5C. These Gibbs free energies would then be used to calculate the Gibbs free energy difference, ΔΔG [TS(1-hexene) - TS(non-1-hexene catalyzed trimerization by-products)], for each branched decene and / or dodecene used in the trimerization cycle selectivity calculation to 1-hexene.

[0223] A mathematical relationship is then determined between the calculated Gibbs free energy difference ΔΔG[TS(1-hexene)-TS(branched decene or branched dodecene)] and the natural logarithm of a set of heteroatom ligand-metal compound complexes for the experimentally determined 1-hexene to branched decene or dodecene ratios for each branched decene and / or dodecene utilized in the calculation of trimerization cycle selectivity to 1-hexene. This mathematical relationship can then be used to determine the non-experimentally determined amount of 1-hexene and each branched decene and / or dodecene utilized in the calculation of trimerization cycle selectivity to 1-hexene via interpolation and extrapolation for the calculated Gibbs free energy difference ΔΔG[TS(1-hexene)-TS(branched decene or branched dodecene)] where the experimental amounts of 1-hexene and each branched decene and / or dodecene are unknown.

[0224] A second non-limiting method for determining trimerization cycle selectivity to 1-hexene (either based on all non-1-hexene catalyzed trimerization by-products or based on specific / specific non-1-hexene catalyzed trimerization by-products) would be to replace the moles of 1-hexene and the moles of each non-1-hexene catalyzed trimerization by-product with their respective corresponding calculated activities / productivities as determined by turnover frequency calculations for 1-hexene and each non-1-hexene catalyzed trimerization by-product utilized in the calculation of trimerization cycle selectivity to 1-hexene. For example, if one were to determine trimerization cycle selectivity to 1-hexene based on the moles of 1-hexene and the moles of branched decene and / or branched dodecene produced when 1-hexene and / or 1-octene participate in a trimerization catalytic cycle, one would 1) replace the moles of 1-hexene produced with the calculated activity / productivity determined by turnover frequency calculations using all ground states and transition states in the GS-II / GS-III / GS-IV / GS-VI / TS-III pathway, and 2) replace the moles for each branched decene and / or branched dodecene produced with the appropriate calculated activity / productivity determined by turnover frequency calculations for each branched decene and / or branched dodecene produced using all ground states and transition states in the GS-IIa / GS-IIIa / GS-IVa / GS-VIa / TS-IIIa pathway and / or in the GS-IIb / GS-IIIb / GS-IVb / GS-VIb / TS-IIIb pathway. If other non-1-hexene catalyzed trimerization by-product(s) are included in determining the trimerization cycle selectivity to 1-hexene, the number of moles of these other non-1-hexene catalyzed trimerization by-product(s) would be substituted for the calculated activity / productivity determined using rotational frequency calculations using all ground and transition states in the pathway appropriate for the non-1-hexene catalyzed trimerization by-product(s).

[0225] Tetramerization cycle selectivity to 1-octene (either based on all non-1-octene catalyzed tetramerization by-products or based on specific / specific non-1-octene catalyzed trimerization by-products) can be determined using different methods described herein.

[0226] In a first, non-limiting method, the amounts of 1-octene and non-1-octene-catalyzed tetramerization by-products can be determined from the ratio of non-1-octene-catalyzed tetramerization by-products to 1-octene. In this method, the ratio of non-1-octene-catalyzed tetramerization by-products to 1-hexene for each non-1-octene-catalyzed tetramerization by-product, which is the basis for the tetramerization cycle selectivity to 1-octene, is determined by determining the Gibbs free energy difference ΔΔG between 1) the rate-limiting transition state / reaction step leading to 1-octene production and 2) the rate-limiting transition state / reaction step leading to the non-1-octene-catalyzed tetramerization by-product. This Gibbs free energy difference can then be used to determine the amounts of 1-octene and non-1-octene-catalyzed trimerization by-products from a plot of the calculated Gibbs free energy difference ΔΔG [TS(1-octene) - TS(non-1-octene-catalyzed tetramerization by-product)] versus the experimentally determined Gibbs free energy difference of 1-octene and non-1-octene-catalyzed trimerization by-products and the natural logarithm of a set of heteroatom ligand-metal compound complexes for which the experimentally determined amounts are known. It should be noted that the transition states / reaction steps that determine the selectivity of the tetramerization catalytic cycle are not predetermined and can only be determined by performing the necessary calculations on the tetramerization catalytic cycle, and the specific transition states / reaction steps that determine selectivity may be ligand-dependent.

[0227] As an example, tetramerization cycle selectivities to 1-octene based on branched dodecene and / or tetradecene can be calculated using the proposed tetramerization reaction pathways illustrated in Figure 5A (GS-II / GS-III / GS-IV / GS-VI / GS-V / TS-IV / GS-VII / TS-V via the octene pathway), Figure 5B (GS-IIa / GS-IIIa / GS-IVa / GS-VIa / GS-Va / TS-IVa / GS-VIIa / TS-Va via the branched dodecene or tetradecene pathway), and Figure 5C (GS-IIb / GS-IIIb / GS-IVb / GS-VIb / GS-Vb / TS-IVb / GS-VIIb / TS-Vb via the branched dodecene or tetradecene pathway). In this example, one would calculate 1) the Gibbs free energy of the rate-limiting transition state / reaction step for 1-octene production as depicted in Figure 5A, 2) the Gibbs free energy of the rate-limiting step / reaction step for each branched dodecene and / or branched tetradecene produced in the tetramerization cycle as depicted in Figure 5B, and 3) the Gibbs free energy of the rate-limiting step / reaction step for each branched dodecene and / or branched tetradecene produced in the trimerization cycle as depicted in Figure 5C. These Gibbs free energies would then be used to calculate the Gibbs free energy difference, ΔΔG [TS(1-octene) - TS(non-1-octene catalyzed trimerization by-products)], for each branched dodecene and / or tetradecene used in the trimerization cycle selectivity calculation to 1-hexene. Then, for each branched dodecene and / or tetradecene utilized in the calculation of tetramerization cycle selectivity to 1-octene, a mathematical relationship is determined between the calculated Gibbs free energy difference ΔΔG [TS(1-octene)−TS(branched dodecene or branched tetradecene)] and the natural logarithm of a set of heteroatom ligand-metal compound complexes for the experimentally determined 1-octene to branched dodecene or tetradecene ratio.This mathematical relationship is then used to determine the non-experimentally determined amount of 1-octene and the amount of each branched dodecene and / or tetradecene used in calculating the tetramerization cycle selectivity to 1-octene via interpolation and extrapolation to the calculated Gibbs free energy difference ΔΔG[TS(1-octene)−TS(branched dodecene or branched tetradecene)] where the experimental amounts of 1-octene and each branched dodecene and / or tetradecene are not known.

[0228] A second non-limiting method for determining the tetramerization cycle selectivity to 1-octene (either based on all non-1-octene catalyzed tetramerization by-products or based on specific / specific non-1-octene catalyzed tetramerization by-products) would be to replace the moles of 1-octene and the moles of each non-1-octene catalyzed tetramerization by-product with their respective corresponding calculated activities / productivities determined using turnover frequency calculations for 1-octene and each non-1-octene catalyzed tetramerization by-product utilized in the calculation of the tetramerization cycle selectivity to 1-octene. For example, if one were to determine the tetramerization cycle selectivity to 1-octene based on the number of moles of 1-octene produced and the number of moles of branched dodecene and / or branched tetradecene produced when 1-hexene and / or 1-octene participate in the tetramerization catalytic cycle, one could: 1) calculate the number of moles of 1-octene produced by a rotational frequency calculation using all ground and transition states in the GS-II / GS-III / GS-IV / GS-VI / GS-V / TS-IV / GS-VII / TS-V pathway; and 2) the number of moles for each branched dodecene and / or branched tetradecene produced will be replaced with the appropriate calculated activity / productivity determined by turnover frequency calculations using all ground states and transition states in the GS-IIa / GS-IIIa / GS-IVa / GS-VIa / GS-Va / TS-IVa / GS-VIIa / TS-Va pathway and / or in the GS-IIb / GS-IIIb / GS-IVb / GS-VIb / GS-Vb / TS-IVb / GS-VIIb / TS-Vb pathway. If other non-1-octene catalyzed tetramerization by-product(s) are included in the determination of tetramerization cycle selectivity to 1-octene, the number of moles of these other non-1-octene catalyzed tetramerization by-product(s) will be replaced with the calculated activity / productivity determined using turnover frequency calculations using all ground states and transition states in the pathway appropriate for the non-1-octene catalyzed tetramerization by-product(s).

[0229] With respect to olefin purity, where the relevant performance parameter for an olefin oligomerization reaction is 1-hexene purity, Figure 6 illustrates the pathways by which 1-hexene may be formed and the pathways by which a 6-carbon impurity may be generated in the production of 1-hexene. The ground state and transition state designations correspond to the ground state and transition state structures disclosed herein. With reference to this diagram, 1-hexene (C6) may be generated, for example, via the following pathways: [1] GS-VI → TS-III, [2] GS-VI → TS-VI → GS-VIII → TS-VII, and [3] GS-VI → TS-XIII → GS-XI → TS-XIV. In a further embodiment, in FIG. 6 , the 1-hexene (C6) impurity can arise, for example, via the following pathways: [1] GS-VI → TS-VI → GS-VIII → TS-VIII → GS-IX → TS-IX, [2] GS-VI → TS-VI → GS-VIII → TS-VIII → GS-IX → TS-X → GS-X → TS-XI, [3] GS-VI → TS-VI → GS-VIII → TS-VIII → GS-IX → TS-X → GS-X → TS-XII, and [4] GS-VI → TS-XV.

[0230] In this embodiment, Figure 6 illustrates various collections of ground and transition states that can control the selectivity to produce 1-hexene versus a 6-carbon impurity or (1-hexene impurity). This concept is illustrated in Figure 7, where the energy difference of the transition states (TS) controls the pathway to 1-hexene and the pathway to the C6 impurity (1-hexene impurity).

[0231] Thus, with respect to olefin purity, specifically "1-hexene purity," if the performance parameter relevant to an olefin oligomerization reaction is 1-hexene purity, [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes. A1 , …GS Ap GS I -VI, GS I -VIII, GS I -IX, GS I -X, GS I-XI, or any combination thereof, and may be independently selected therefrom; [2] a plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; A1 , T.S. A2 , …TS Am TS I -III, TS I -VI, TS I -VII, TS I -VIII, TS I -IX, TS I -X, TS I -XI, TS I -XII, TS I -XIII, TS I -XIV, TS I -XV, or any combination thereof, and may be independently selected therefrom; [3] one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; B1 , …GS Bp GS I -VI, GS I -VIII, GS I -IX, GS I -X, GS I -XI, or any combination thereof, and / or [4] a plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 , T.S. B2 , …TS Bm TS I -III, TS I -VI, TS I -VII, TS I -VIII, TS I -IX, TS I -X, TS I -XI, TS I -XII, TS I -XIII, TS I -XIV, TS I-XV, or any combination thereof. One method for determining 1-hexene purity can be based on the mass ratio of 1-hexene to the sum of other (non-1-hexene) C6 products, calculated as ln[(1-hexene mass) / (non-1-hexene C6 mass)] to ΔΔG[TS(1-hexene)-TS(non-1-hexene C6)].

[0232] Another method for determining 1-hexene purity may involve separately determining the 1-hexene activity / productivity for each 1-hexene pathway in Figure 6, separately determining the activity / productivity for each C6 impurity produced by the pathways in Figure 6, and determining the percentage that the sum of all 1-hexene activities / productivities represents of the sum of all 1-hexene activities / productivities plus the sum of all C6 impurities activities / productivities. The activity / productivity for each 1-hexene production pathway and each C6 impurity production pathway in Figure 6 may be a calculated activity / productivity as calculated / determined / estimated by the methods described herein (e.g., via determining the turnover frequency for all 1-hexene production pathways and all C6 production pathways in Figure 6).

[0233] Regarding "1-octene purity," if the performance parameter related to the olefin oligomerization reaction is 1-octene purity, [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes A1 , …GS Ap GS I -VII, GS I -XII, GS I -XIII, or any combination thereof, and / or [2] one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex. B1 , …GS Bp GS T -VII, GS T -XII, GS T-XIII, or any combination thereof. When one or more performance parameters include or are selected from 1-octene purity, it can be determined based on the mass ratio of 1-octene to the sum of other (non-1-octene) C8 products and calculated as ln[(1-octene mass) / (non-1-octene C8 mass)] vs. ΔG[TS(1-octene)-TS(non-1-octene C8)].

[0234] Reviewing Figures 5C and 6, it can be seen that not all addition of the fourth ethylene leads to the production of 1-octene. For example, in Figure 6, it can be seen that ethylene can a) complex with GS-IX to form methylenecyclopentane via the GS-IX / TS-X / GS-X / TS-XII pathway, and / or 2) form methylcyclopentane and ethylene via the GS-IX / TS-X / GS-X / TS-XI pathway, and / or b) complex with GS-VI to form 1-hexene and ethane via the GS-VI / TS-XIII / GS-XI / TS-XIV pathway. Therefore, these pathways lead to inefficiency of the fourth ethylene addition in olefin tetramerization. Therefore, a specific parameter associated with olefin oligomerization reactions may be the 1-octene efficiency of the fourth ethylene addition.

[0235] The 1-octene efficiency of the fourth ethylene addition can be determined as the number of moles of 1-octene produced via the fourth ethylene addition divided by the number of moles of 1-octene produced plus one or more of the moles of methylenecyclopentane, methylcyclopentane, and / or 1-hexene produced. Any one or more of the moles of methylenecyclopentane, methylcyclopentane, and 1-hexene can be utilized in calculating the 1-octene efficiency of the fourth ethylene addition and can be determined based on the relative moles of methylenecyclopentane, methylcyclopentane, or 1-hexene produced by the fourth ethylene addition.

[0236] The methods described herein can be used to determine the 1-octene efficiency of the fourth ethylene addition. One specific, non-limiting method would be to replace the moles of 1-octene and methylenecyclopentane, methylcyclopentane, and / or 1-hexene with their activities / productivities as determined by rotational frequency calculations described herein. In this method, 1) the moles of 1-octene are replaced with the calculated ac...

Claims

1. 1. A method for designing heteroatom ligand-metal compound complexes for olefin oligomerization, said method comprising: (a) n input variables I １ , I ２ , …I ｎ (n is an integer), where each input variable is selected from one or more ground state model structures GS Ａ１ , ...GS Ａｐ (p is an integer), and a plurality of transition state model structures TS associated with said one or more ground state model structures. Ａ１ , T.S. Ａ２ , ...TS Ａｍ (m is an integer), said one or more ground state model structures GS Ａ１ , ...GS Ａｐ and each of the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ are derived from one or more first training heteroatom ligand-metal compound complexes, each complex comprising a first training heteroatom ligand; (b) the ground state model structure GS Ａ１ , ...GS Ａｐ and the transition state model structure TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ For each of the n input variables I １ , I ２ , …I ｎ assigning a quantitative value to (c) by at least one processor of the device, generating the ground state model structure GS Ａ１ , ...GS Ａｐ and the transition state model structure TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ determining the relative energies of each of (d) Each of the n input variables I １ , I ２ , …I ｎ and the ground state model structure GS Ａ１ , ...GS Ａｐ and the transition state model structure TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ generating a machine learning model based on the correlation of each of the relative energies of (e) Based on the machine learning model, [1] the ground state model structure GS Ａ１ , ...GS Ａｐ and one of the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ [2] the difference in energy between at least one of the plurality of transition state model structures TS [ΔG(TS-GS) or ΔΔG(TS-GS)] Ａ１ , T.S. Ａ２ , ...TS Ａｍ The n input variables I are associated with the energy difference [ΔG(TS-TS) or ΔΔG(TS-TS)] between any two or more of １ , I ２ , …I ｎ and identifying one or more of: (f) the one or more n input variables I identified from step (e). １ , I ２ , …I ｎ and forming first target heteroatom ligand-metal compound complexes for olefin oligomerization, each of the first target heteroatom ligand-metal compound complexes having one or more ground state model structures G5 Ｂ１ , ...GS Ｂｘ (x is an integer), or a plurality of transition state model structures TS associated with said one or more ground state model structures. Ｂ１ , T.S. Ｂ２ , ...TS Ｂｙ n output variables O having quantitative values ​​corresponding to any of the structural or electronic properties of １ , O ２ , ...O ｎ is characterized by said one or more ground state model structures GS Ｂ１ , ...GS Ｂｘ and each of the plurality of transition state model structures TS Ｂ１ , T.S. Ｂ２ , ...TS Ｂｙ are derived from said first target heteroatom ligand-metal compound complex, each complex comprising a first target heteroatom ligand; (g) identifying one or more performance parameters associated with an olefin oligomerization reaction and values ​​of said performance parameters for said one or more first training heteroatom ligand-metal compound complexes and said first target heteroatom ligand-metal compound complex; (h) calculating the n output variables O of the first target heteroatom ligand-metal compound complex; １ , O ２ , ...O ｎ The quantitative value of is calculated based on n new input variables I derived from one or more second training heteroatom ligand-metal compound complexes containing the second training heteroatom ligand for olefin oligomerization. １．１ , I ２．１ , …I ｎ．１ repeating steps (a) through (f) one or more times using as an input data set n of n output variables O, wherein the input data set is computationally evaluated against the machine learning model to generate a second target heteroatomic ligand-metal compound complex comprising a second target heteroatomic ligand, and the second target heteroatomic ligand-metal compound complex is １．１ , O ２．１ , ...O ｎ．１ and a performance parameter value of one or more second target heteroatom ligand-metal compound complexes; Including, the one or more ground state model structures and the plurality of transition state model structures; 【Chemistry 3a】 (In the formula, R 1 is hydrogen or a C 1 -C 20 organyl group; R 2 is a C 1 -C 20 organyl group; T is oxygen or sulfur; R 2a and R 2b are independently a C 1 -C 20 organyl group; L 12 and L 23 are independently a C 2 -C 20 organylene group; L 22 is a C 3 -C 20 organylene group; R 3 is hydrogen or a C 1 -C 20 organyl group; R 4 and R 5 are independently hydrogen or a C 1 -C 20 organyl group; R 1 and R 2 optionally join to form L 12r , where L 12r is a C 3 -C 30 organylene group; R 4 and R 5 optionally join to form L 45 , where L 45 is a C 4 -C 30 organylene group; "*" represents any additional bond required in [1] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes, or [2] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes. From, as well as, 【Chemistry 4a】 (In the formula, each R 1s , R 2s , R 5s , R 11s , R 12s , R 13s , and R 14s is independently selected from hydrogen or a C 1 -C 20 organyl group; each L 1s , L 3s , and L 4s is independently selected from a C 2 -C 20 organylene group; any two geminal R 1s optionally join to form L 11s , where L 11s is a C 2 -C 30 organylene group; any two geminal R 2s optionally join to form L 22s , where L 22s is a C 2 -C 30 organylene group; any geminal R 11s and R 12s optionally join to form L 12s , where L 12s is a C 2 -C 30 organylene group; any geminal R 13s and R 14s optionally join to form L 34s , where L 34s is a C 2 -C 30 organylene group; "*" represents any additional bond required in [1] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes, or [2] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes. comprising a chromium heteroatom ligand moiety independently selected from The method.

2. (i) [1] synthesizing the first target heteroatom ligand and / or the second target heteroatom ligand, or [2] synthesizing the first target heteroatom ligand and / or the second target heteroatom ligand, followed by synthesizing the first target heteroatom ligand-metal compound complex or the second target heteroatom ligand-metal compound complex. The method of claim 1 further comprising:

3. (j) performing an oligomerization reaction of the olefin by [1] contacting the first target heteroatom ligand or the second target heteroatom ligand, a metal compound, an organometallic compound, and an olefin, or [2] contacting the first target heteroatom ligand-metal compound complex or the second target heteroatom ligand-metal compound complex, an organometallic compound, and an olefin. The method of claim 2 further comprising:

4. The n input variables I identified in step (e) １ , I ２ , …I ｎ The one or more of the n input variables I affect ΔG(TS-GS), ΔΔG(TS-GS), or ΔΔG(TS-TS). １ , I ２ , …I ｎ [1] for each percentage change in said one or more of said one or more ground state model structures GS Ａ１ , ...GS Ａｐ and the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ [2] the energy difference [ΔG(TS-GS) or ΔΔG(TS-GS)] between at least one of the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ 2. The method of claim 1, wherein the difference in energy between any two or more of the two is determined based on a greater percentage change in the difference in energy [ΔG(TS-TS) or ΔΔG(TS-TS)].

5. said one or more first training heteroatom ligand-metal compound complexes comprising: [(HetLig)CrX ｑ L ｒ ] ３－ｑ (A) having a formula independently selected from: HetLig represents the one or more first training heteroatom ligands; X is an anionic ligand and q is an integer; L is a neutral ligand and r is an integer; Any two or more of the X ligands and the L ligands may be linked to form a multidentate ligand; Each of the selected n input variables I １ , I ２ , …I ｎ is one or more ground state model structures GS of formula (A) Ａ１ , ...GS Ａｐ or the plurality of transition state model structures TS associated with the one or more ground state model structures. Ａ１ , T.S. Ａ２ , ...TS Ａｍ corresponding to any of the structural or electronic properties of The method of claim 1.

6. The one or more first training heteroatom ligand-metal compound complexes (GS Ｉ ) the one or more ground state model structures GS Ａ１ , ...GS Ａｐ and the one or more first target heteroatom ligand-metal compound complexes (GS Ｔ ) the one or more ground state model structures GS Ｂ１ , ...GS Ｂｘ but, 【Chemistry 1】 are independently selected from During the ceremony, HetLig represents the one or more first training heteroatom ligands or the one or more first target heteroatom ligands; GS Ｘ The first training heteroatom ligand-metal compound complex (GS Ｉ ) or the first target heteroatom ligand-metal compound complex (GS Ｔ ) The method of claim 1.

7. The one or more first training heteroatom ligand-metal compound complexes (TS Ｉ ) the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ and the one or more first target heteroatom ligand-metal compound complexes (TS Ｔ ) the plurality of transition state model structures TS Ｂ１ , T.S. Ｂ２ , ...TS Ｂｙ but, 【Chemistry 2】 are independently selected from During the ceremony, HetLig represents the one or more first training heteroatom ligands or the one or more first target heteroatom ligands; TS Ｙ the first training heteroatom ligand-metal compound complex (TS Ｉ ) or the first target heteroatom ligand-metal compound complex (TS Ｔ ) The method of claim 6.

8. any one of the one or more ground state model structures and the plurality of transition state model structures; 【Transformation 3】 and During the ceremony, R １ is hydrogen or C １ ~C ２０ is an organyl group, R ２ But C １ ~C ２０ is an organyl group, T is oxygen or sulfur; R ２ａ and R ２ｂ became independent and C １ ~C ２０ is an organyl group, L １２ and L ２３ became independent and C ２ ~C ２０ is an organylene group, L ２２ But C ３ ~C ２０ is an organylene group, R ３ is hydrogen or C １ ~C ２０ is an organyl group, R ４ and R ５ are independently hydrogen or C １ ~C ２０ is an organyl group, R １ and R ２ optionally joined to form L １２ｒ Forming L １２ｒ But C ３ ~C ３０ is an organylene group, R ４ and R ５ optionally joined to form L ４５ Forming L ４５ But C ４ ~C ３０ is an organylene group, " ＊ represents any additional bond required in [1] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes, or [2] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes, The method of claim 1.

9. R １ But hydrogen, C １ ~C ２０ a hydrocarbyl group, or C １ ~C ２０ is a heterohydrocarbyl group, R ２ But C １ ~C ２０ Hydrocarbyl group or C １ ~C ２０ is a heterohydrocarbyl group, R ２ａ and R ２ｂ became independent and C １ ~C ２０ Hydrocarbyl group or C １ ~C ２０ heterohydrocarbyl groups, L １２ and L ２３ became independent and C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ heterohydrocarbylene groups; L ２２ But C ３ ~C ２０ Hydrocarbylene group or C ３ ~C ２０ is a heterohydrocarbylene group, R ３ But hydrogen, C １ ~C ２０ a hydrocarbyl group, or C １ ~C ２０ is a heterohydrocarbyl group, R ４ and R ５ became independent and C １ ~C ２０ Hydrocarbyl group or C １ ~C ２０ heterohydrocarbyl groups, R １ and R ２ optionally joined to form L １２ｒ Forming L １２ｒ But C ３ ~C ２０ Hydrocarbylene group or C ３ ~C ２０ is a heterohydrocarbylene group, R ４ and R ５ optionally joined to form L ４５ Forming L ４５ But C ４ ~C ２０ Hydrocarbylene group or C ４ ~C ２０ is a heterohydrocarbylene group, The method of claim 8.

10. The n input variables I １ , I ２ , …I ｎ but the following variables: (a) Cr-P distance (Å), (b) Cr-N distance (Å), (c) R-to-R distance on Cr---α-C (Å), (d) P-Cr-N angle (degrees), (e) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to or within bonding distance of said Cr atom; (f) Cr-N-C angle (degrees), (g) distance from the pocket R(Cr-N 1 )·sin(∠Cr-N 1 −P) (Å); (h) Cr---α-C distance (Å), (i) Cr CHELPG (atomic charge), (j) P CHELPG (atomic charge), (k) N CHELPG (atomic charge), (l) Cr-N-CN dihedral angle (degrees), (m) Cr-PNC dihedral angle (degrees), (n) P-Cr-N-C dihedral angle (degrees), (o) P-N-CN dihedral angle (degrees), (p) the C-C-N-C dihedral angle (degrees), or (q) the buried volume percent, defined as the extent to which the first coordination sphere of the Cr metal center is occupied by (P,N) heteroatom ligands, as used in Nat. Chem. 2019, 11(10), 872-879; 9. The method of claim 8, comprising or selected from any one or more of:

11. any one of the one or more ground state model structures and the plurality of transition state model structures; 【Chemistry 4】 and During the ceremony, Each R １ｓ , R ２ｓ , R ５ｓ , R １１ｓ , R １２ｓ , R １３ｓ , and R １４ｓ are independently hydrogen or C １ ~C ２０ is selected from organyl groups, Each L １ｓ , L ３ｓ , and L ４ｓ became independent and C ２ ~C ２０ organylene groups, Any two geminal R １ｓ optionally joined to form L １１ｓ Forming L １１ｓ However, C2 to C ３０ is an organylene group, Any two geminal R ２ｓ optionally joined to form L ２２ｓ Forming L ２２ｓ However, C2 to C ３０ is an organylene group, Any geminal R １１ｓ and R １２ｓ optionally joined to form L １２ｓ Forming L １２ｓ However, C2 to C ３０ is an organylene group, Any geminal R １３ｓ and R １４ｓ optionally joined to form L ３４ｓ Forming L ３４ｓ However, C2 to C ３０ is an organylene group, " ＊ represents any additional bond required in [1] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes, or [2] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes, The method of claim 1.

12. Each R １ｓ , R ２ｓ , R ５ｓ , R １１ｓ , R １２ｓ , R １３ｓ , and R １４ｓ are independently hydrogen, C １ ~C ２０ a hydrocarbyl group, or C １ ~C ２０ heterohydrocarbyl groups, Each L １ｓ , L ３ｓ , and L ４ｓ became independent and C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ heterohydrocarbylene groups; Any two geminal R １ｓ optionally joined to form L １１ｓ Forming L １１ｓ But C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ is a heterohydrocarbylene group, Any two geminal R ２ｓ optionally joined to form L ２２ｓ Forming L ２２ｓ But C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ is a heterohydrocarbylene group, Any geminal R １１ｓ and R １２ｓ optionally joined to form L １２ｓ Forming L １２ｓ But C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ is a heterohydrocarbylene group, Any geminal R １３ｓ and R １４ｓ optionally joined to form L ３４ｓ Forming L ３４ｓ But C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ is a heterohydrocarbylene group, The method of claim 11.

13. The n input variables I １ , I ２ , …I ｎ but the following variables: (a) the first, second, or third Cr-N distance (Å); (b) the first, second, or third Cr-P distance (Å); (c) the first or second Cr-S distance (Å); (d) any one or more N-Cr-N angles (degrees); (e) any one or more P-Cr-P angles (degrees); (f) any one or more S-Cr-S angles (degrees); (g) any one or more S-Cr-N angles (degrees); (h) any one or more N—Cr—P angles (degrees); (i) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to or within bonding distance of said Cr atom; (j) C-Cr-P angle (degrees), (k) C-Cr-S angle (degrees), (l) Cr-N-C angle (degrees), (m) Cr-P-C angle (degrees), (n) Cr-S-C angle (degrees), (o) Cr-P-C angle (degrees), (p) Cr---α-C inter-R distance (Å), (q) distance from the pocket R(Cr-N 1 )·sin(∠Cr-N 1 −P) (Å); (r) Cr---α-C distance (Å), (s) Cr CHELPG (atomic charge), (t) any P CHELPG (atomic charges), (u) any N CHELPG (atomic charges), (v) any chelate Cr-N-C-C dihedral angle (degrees); (w) any chelate Cr-P-C-C dihedral angle (degrees); (x) any chelate Cr-S-C-C dihedral angle (degrees), or (y) buried volume percent, defined as the extent to which the first coordination sphere of the Cr metal center is occupied by (P,N) heteroatom ligands, as used in Nat. Chem. 2019, 11(10), 872-879; 12. The method of claim 11, comprising or selected from any one or more of:

14. The one or more performance parameters associated with the olefin oligomerization reaction are (a) 1-hexene purity, (b) 1-octene purity, (c) 1-hexene:1-octene ratio (C ６ / C ８ (d) 1-hexene productivity; (e) 1-octene productivity; (f) total productivity of 1-hexene and 1-octene; or any combination thereof.

15. (a) [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ But, GS Ｉ -I, G.S. Ｉ -II, GS Ｉ -III, GS Ｉ -IV, GS Ｉ -V, GS Ｉ -VI, GS Ｉ -VII, or any combination thereof, and [2] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes. Ａ１ , T.S. Ａ２ , ...TS Ａｍ But, TS Ｉ -I, T.S. Ｉ -II, TS Ｉ -III, TS Ｉ -IV, TS Ｉ -V, or any combination thereof; (b) [1] the one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ ,...GSBx is GS Ｔ -I, G.S. Ｔ -II, GS Ｔ -III, GS Ｔ -IV, GS Ｔ -V, GS Ｔ -VI, GS Ｔ [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex, Ｂ１ , T.S. Ｂ２ , ...TSBy, TS Ｔ -I, T.S. Ｔ -II, TS Ｔ -III, TS Ｔ -IV, TS Ｔ -V, or any combination thereof; (c) the performance parameter related to the olefin oligomerization reaction is the 1-hexene productivity, the 1-octene productivity, or the total productivity of 1-hexene and 1-octene of the heteroatom ligand-metal compound complex; The method of claim 7.

16. (a) [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ But, GS Ｉ [2] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , T.S. Ａ２ , ...TS Ａｍ But, TS Ｉ -III and TS Ｉ - IV, (b) [1] the one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ ,...GSBx is GS Ｔ [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ , T.S. Ｂ２ , ...TSBy, TS Ｔ -III and TS Ｔ - IV, (c) the performance parameter associated with the olefin oligomerization reaction is C ６ / C ８ The ratio is The method of claim 7.

17. (a) [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ But, GS Ｉ -VI, GS Ｉ -VIII, G.S. Ｉ -IX, GS Ｉ -X, GS Ｉ -XI, or any combination thereof, and [2] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes. Ａ１ , T.S. Ａ２ , ...TS Ａｍ But, TS Ｉ -III, TS Ｉ -VI, TS Ｉ -VII, TS Ｉ -VIII, TS Ｉ -IX, TS Ｉ -X, TS Ｉ -XI, TS Ｉ -XII, TS Ｉ -XIII, TS Ｉ -XIV, TS Ｉ -XV, or any combination thereof; (b) [1] the one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ , ...GSBx comprises or is independently selected from GST-VI, GST-VIII, GST-IX, GST-X, GST-XI, or any combination thereof, and [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. Ｂ１ , T.S. Ｂ２ , ...TSBy includes or is selected from TST-III, TST-VI, TST-VII, TST-VIII, TST-IX, TST-X, TST-XI, TST-XII, TST-XIII, TST-XIV, TST-XV, or any combination thereof; (c) the performance parameter related to the olefin oligomerization reaction is 1-hexene purity; The method of claim 7.

18. (a) [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ But, GS Ｉ -VII, GS Ｉ -XII, GS Ｉ [2] the one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ ,...GSBx is GS Ｔ -VII, GS Ｔ -XII, GS Ｔ -XIII, or any combination thereof; (b) the performance parameter related to the olefin oligomerization reaction is 1-octene purity; The method of claim 7.

19. (a) [1] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , T.S. Ａ２ , ...TS Ａｍ is the ground state model structure GS Ｉ Addition of the olefin to -VI gives the ground state model structure GS Ｉ and / or [2] a plurality of transition state model structures TS derived from one or more first target heteroatom ligand-metal compound complexes. Ｂ１ , T.S. Ｂ２ , ...TSBy is the ground state model structure GS Ｔ Addition of the olefin to -VI gives the ground state model structure GS Ｔ -VII, or (b) [1] the plurality of transition state model structures TS derived from the first training heteroatom ligand-metal compound complex; Ａ１ , T.S. Ａ２ , ...TS Ａｍ However, the transition state TS Ｉ and / or [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. Ｂ１ , T.S. Ｂ２ , ...TSBy is the transition state TS Ｔ - IV, The method of claim 7.

20. (a) [1] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , T.S. Ａ２ , ...TS Ａｍ is the ground state model structure GS Ｉ Transition state and / or ground state model structure GS for β-H abstraction from β-VI to produce 1-hexene Ｉ [0022] [0023] [0024] [0025] [0026] [0027] [0028] [0029] [0030] [0029] [0031] [0029] [0032] [0033] [0029] [0034] [0035] [0036] [0037] [0038] [0039] [ Ｂ１ , T.S. Ｂ２ , ...TSBy is the ground state model structure GS Ｔ Transition state and / or ground state model structure GS for β-H abstraction from β-VI to produce 1-hexene Ｔ -VII by β-H abstraction to produce 1-octene, (b) [1] the plurality of transition state model structures TS derived from the first training heteroatom ligand-metal compound complex; Ａ１ , T.S. Ａ２ , ...TS Ａｍ But, TS Ｉ -III or TS Ｉ and / or [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. Ｂ１ , T.S. Ｂ２ , ...TSBy, TS Ｔ -III or TS Ｔ -including V, The method of claim 7.

21. the one or more ground state model structures GS derived from the one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ and each of the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ For each of the n input variables I １ , I ２ , …I ｎ 2. The method of claim 1, wherein the quantitative value assigned to is assigned based on a calculated value, a measured value, or an estimated value, or any combination thereof.

22. said step of forming said second target heteroatom ligand-metal compound complex comprises: (a) one or more n input variables I １ , I ２ , …I ｎ , or I １．１ , I ２．１ , …I ｎ．１ and converting the quantitative value of n to a corresponding n output variables O in any first training heteroatom ligand-metal compound complex comprising a chromium heteroatom ligand moiety independently selected from NPFCrM-1, NPACrM-1, GuCrM-1, GuCrM-2, GuCrM-3, GuCrM-4, GuCrM-5, or HCPACrM-1. １ , O ２ , ...O ｎ , or O １．１ , O ２．１ , ...O ｎ．１ To approach the value of [1] Group R １ , R ２ , L １２ｒ , R ２ａ , R ２ｂ , L １２ , L ２３ , L ２２ , R ３ , R ４ , R ５ , and L ４５ Independently increasing or decreasing the steric volume of one or more of [2] The group R １ , R ２ , L １２ｒ , R ２ａ , R ２ｂ , L １２ , L ２３ , L ２２ , R ３ , R ４ , R ５ , and L ４５ Independently varying one or more of the induced electronic effects of [3] independently increasing or decreasing the degree of saturation in one or more of the organyl or organylene groups; [4] Increasing or decreasing the polarity of the solvent used in the oligomerization of olefins, or [5] any combination thereof; and adjusting by (b) generating a second target heteroatom ligand-metal compound complex for olefin oligomerization, the second target heteroatom ligand comprising the second target heteroatom ligand, based on the at least one adjusted n input variables from step (a); The method of claim 1 , comprising:

23. said step of forming said second target heteroatom ligand-metal compound complex comprises: (a) one or more n input variables I １ , I ２ , …I ｎ , or I １．１ , I ２．１ , …I ｎ．１ and calculating the corresponding n output variables O in any first training heteroatom ligand-metal compound complex comprising a chromium heteroatom ligand moiety independently selected from NRNCrM-1, PRPCrM-1, SRSCrM-1, PNPCrM-1, NRNRNCrM-1, PRPRPCrM-1, SRNRSCrM-1, PRNRPCrM-1, or NRPRNCrM-1. １ , O ２ , ...O ｎ , or O １．１ , O ２．１ , ...O ｎ．１ To approach the value of [1] Group R １ｓ , R ２ｓ , R ５ｓ , R １１ｓ , R １２ｓ , R １３ｓ , R １４ｓ , L １ｓ , L ３ｓ , L ４ｓ , L １ｓｒ , L １ｓｒ , L １２ｓｒ , and L ３４ｓｒ Independently increasing or decreasing the steric volume of one or more of [2] The group R １ｓ , R ２ｓ , R ５ｓ , R １１ｓ , R １２ｓ , R １３ｓ , R １４ｓ , L １ｓ , L ３ｓ , L ４ｓ , L １ｓｒ , L １ｓｒ , L １２ｓｒ , and L ３４ｓｒ Independently varying one or more of the induced electronic effects of [3] independently increasing or decreasing the degree of saturation in one or more of the organyl or organylene groups; [4] Increasing or decreasing the polarity of the solvent used in the oligomerization of olefins, or [5] any combination thereof; and adjusting by (b) generating a second target heteroatom ligand-metal compound complex for olefin oligomerization, the second target heteroatom ligand comprising the second target heteroatom ligand, based on the at least one adjusted n input variables from step (a); The method of claim 1 , comprising:

24. 1. A method for designing heteroatom ligand-metal compound complexes for olefin oligomerization, said method comprising: (a) n input variables I １ , I ２ , …I ｎ (n is an integer), where each input variable is selected from one or more ground state model structures GS Ａ１ , ...GS Ａｐ (p is an integer), and a plurality of transition state model structures TS associated with said one or more ground state model structures. Ａ１ , T.S. Ａ２ , ...TS Ａｍ (m is an integer), said one or more ground state model structures GS Ａ１ , ...GS Ａｐ and each of the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ are generated from one or more first training heteroatom ligand-metal compound complexes, each complex comprising a first training heteroatom ligand; (b) the ground state model structure GS Ａ１ , ...GS Ａｐ and the transition state model structure TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ For each of the n input variables I １ , I ２ , …I ｎ assigning a quantitative value to (c) by at least one processor of the device, generating the ground state model structure GS Ａ１ , ...GS Ａｐ and the transition state model structure TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ determining the relative energies of each of (d) Each of the n input variables I １ , I ２ , …I ｎ and the ground state model structure GS Ａ１ , ...GS Ａｐ and the transition state model structure TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ generating a machine learning model to correlate the relative energies of each of (e) using the machine learning model to compute the n input variables I １ , I ２ , …I ｎ and [1] one or more of the ground state model structure GS Ａ１ , ...GS Ａｐ and one of the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ [2] the difference in energy between at least one of the plurality of transition state model structures TS [ΔG(TS-GS) or ΔΔG(TS-GS)] Ａ１ , T.S. Ａ２ , ...TS Ａｍ determining the relationship between the energy difference [ΔG(TS-TS) or ΔΔG(TS-TS)] between any two or more of (f) generating an output of the machine learning model based on the relationships identified from step (e), the output including first target heteroatom ligand-metal compound complexes for olefin oligomerization, the first target heteroatom ligand-metal compound complexes each having one or more ground state model structures GSM, ... Ｂ１ , ...GS Ｂｘ (x is an integer), or a plurality of transition state model structures TS associated with said one or more ground state model structures. Ｂ１ , T.S. Ｂ２ , ...TS Ｂｙ n output variables O having quantitative values ​​corresponding to any of the structural or electronic properties of １ , O ２ , ...O ｎ is characterized by said one or more ground state model structures GS Ｂ１ , ...GS Ｂｘ and each of the plurality of transition state model structures TS Ｂ１ , T.S. Ｂ２ , ...TS Ｂｙ are generated from said first target heteroatom ligand-metal compound complex, each complex comprising a first target heteroatom ligand; The n output variables O １ , O ２ , ...O ｎ are new n input variables I １．１ , I ２．１ , …I ｎ．１ and (g) identifying one or more performance parameters associated with an olefin oligomerization reaction and values ​​of said performance parameters for said one or more first training heteroatom ligand-metal compound complexes and said first target heteroatom ligand-metal compound complex; (h) calculating the n output variables O of the first target heteroatom ligand-metal compound complex; １ , O ２ , ...O ｎ The quantitative value of is calculated based on the n new input variables I derived from one or more second training heteroatom ligand-metal compound complexes containing the second training heteroatom ligand for olefin oligomerization. １．１ , I ２．１ , …I ｎ．１ , the new n input variables I １．１ , I ２．１ , …I ｎ．１ repeating steps (a) through (f) one or more times using as an input data set a second target heteroatom ligand-metal compound complex comprising a second target heteroatom ligand, the second target heteroatom ligand-metal compound complex being input to the machine learning model as a set of n new output variables O １．１ , O ２．１ , ...O ｎ．１ and a performance parameter value of one or more second target heteroatom ligand-metal compound complexes; Including, the one or more ground state model structures and the plurality of transition state model structures; 【Chemical Formula 7a】 (In the formula, R 1 is hydrogen or a C 1 -C 20 organyl group; R 2 is a C 1 -C 20 organyl group; T is oxygen or sulfur; R 2a and R 2b are independently a C 1 -C 20 organyl group; L 12 and L 23 are independently a C 2 -C 20 organylene group; L 22 is a C 3 -C 20 organylene group; R 3 is hydrogen or a C 1 -C 20 organyl group; R 4 and R 5 are independently hydrogen or a C 1 -C 20 organyl group; R 1 and R 2 optionally join to form L 12r , where L 12r is a C 3 -C 30 organylene group; R 4 and R 5 optionally join to form L 45 , where L 45 is a C 4 -C 30 organylene group; "*" represents any additional bond required in [1] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes, or [2] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes. From, as well as, 【Chemical Formula 8a】 (In the formula, each R 1s , R 2s , R 5s , R 11s , R 12s , R 13s , and R 14s is independently selected from hydrogen or a C 1 -C 20 organyl group; each L 1s , L 3s , and L 4s is independently selected from a C 2 -C 20 organylene group; any two geminal R 1s optionally join to form L 11s , where L 11s is a C 2 -C 30 organylene group; any two geminal R 2s optionally join to form L 22s , where L 22s is a C 2 -C 30 organylene group; any geminal R 11s and R 12s optionally join to form L 12s , where L 12s is a C 2 -C 30 organylene group; any geminal R 13s and R 14s optionally join to form L 34s , where L 34s is a C 2 -C 30 organylene group; "*" represents any additional bond required in [1] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes, or [2] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes. comprising a chromium heteroatom ligand moiety independently selected from The method.

25. (i) [1] synthesizing the first target heteroatom ligand and / or the second target heteroatom ligand, or [2] synthesizing the first target heteroatom ligand and / or the second target heteroatom ligand, followed by synthesizing the first target heteroatom ligand-metal compound complex or the second target heteroatom ligand-metal compound complex.

25. The method of claim 24, further comprising:

26. (j) performing an oligomerization reaction of the olefin by [1] contacting the first target heteroatom ligand or the second target heteroatom ligand, a metal compound, an organometallic compound, and an olefin, or [2] contacting the first target heteroatom ligand-metal compound complex or the second target heteroatom ligand-metal compound complex, an organometallic compound, and an olefin.

26. The method of claim 25, further comprising:

27. The n input variables I identified in step (e) １ , I ２ , …I ｎ The one or more of the n input variables I affect ΔG(TS-GS), ΔΔG(TS-GS), or ΔΔG(TS-TS). １ , I ２ , …I ｎ [1] for each percentage change in said one or more of said one or more ground state model structures GS Ａ１ , ...GS Ａｐ and the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ [2] the energy difference [ΔG(TS-GS) or ΔΔG(TS-GS)] between at least one of the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ 25. The method of claim 24, wherein the difference in energy between any two or more of the two is determined based on a greater percentage change in the difference in energy [ΔG(TS-TS) or ΔΔG(TS-TS)].

28. said one or more first training heteroatom ligand-metal compound complexes comprising: [(HetLig)CrX ｑ L ｒ ] ３－ｑ (A) having a formula independently selected from: HetLig represents the one or more first training heteroatom ligands; X is an anionic ligand and q is an integer; L is a neutral ligand and r is an integer; Any two or more of the X ligands and the L ligands may be linked to form a multidentate ligand; Each of the selected n input variables I １ , I ２ , …I ｎ is one or more ground state model structures GS of formula (A) Ａ１ , ...GS Ａｐ or the plurality of transition state model structures TS associated with the one or more ground state model structures. Ａ１ , T.S. Ａ２ , ...TS Ａｍ corresponding to any of the structural or electronic properties of 25. The method of claim 24.

29. The one or more first training heteroatom ligand-metal compound complexes (GS Ｉ ) the one or more ground state model structures GS Ａ１ , ...GS Ａｐ and the one or more first target heteroatom ligand-metal compound complexes (GS Ｔ ) the one or more ground state model structures GS Ｂ１ , ...GS Ｂｘ but, 【Transformation 5】 are independently selected from During the ceremony, HetLig represents the one or more first training heteroatom ligands or the one or more first target heteroatom ligands; GS Ｘ The first training heteroatom ligand-metal compound complex (GS Ｉ ) or the first target heteroatom ligand-metal compound complex (GS Ｔ ) 25. The method of claim 24.

30. The one or more first training heteroatom ligand-metal compound complexes (TS Ｉ ) the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ and the one or more first target heteroatom ligand-metal compound complexes (TS Ｔ ) the plurality of transition state model structures TS Ｂ１ , T.S. Ｂ２ , ...TS Ｂｙ but, 【Transformation 6】 are independently selected from During the ceremony, HetLig represents the one or more first training heteroatom ligands or the one or more first target heteroatom ligands; TS Ｙ the first training heteroatom ligand-metal compound complex (TS Ｉ ) or the first target heteroatom ligand-metal compound complex (TS Ｔ ) 30. The method of claim 29.

31. any one of the one or more ground state model structures and the plurality of transition state model structures; 【Transformation 7】 and During the ceremony, R １ is hydrogen or C １ ~C ２０ is an organyl group, R ２ But C １ ~C ２０ is an organyl group, T is oxygen or sulfur; R ２ａ and R ２ｂ became independent and C １ ~C ２０ is an organyl group, L １２ and L ２３ became independent and C ２ ~C ２０ is an organylene group, L ２２ But C ３ ~C ２０ is an organylene group, R ３ is hydrogen or C １ ~C ２０ is an organyl group, R ４ and R ５ are independently hydrogen or C １ ~C ２０ is an organyl group, R １ and R ２ optionally joined to form L １２ｒ Forming L １２ｒ But C ３ ~C ３０ is an organylene group, R ４ and R ５ optionally joined to form L ４５ Forming L ４５ But C ４ ~C ３０ is an organylene group, " ＊ represents any additional bond required in [1] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes, or [2] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes, 25. The method of claim 24.

32. R １ But hydrogen, C １ ~C ２０ a hydrocarbyl group, or C １ ~C ２０ is a heterohydrocarbyl group, R ２ But C １ ~C ２０ Hydrocarbyl group or C １ ~C ２０ is a heterohydrocarbyl group, R ２ａ and R ２ｂ became independent and C １ ~C ２０ Hydrocarbyl group or C １ ~C ２０ heterohydrocarbyl groups, L １２ and L ２３ became independent and C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ heterohydrocarbylene groups; L ２２ But C ３ ~C ２０ Hydrocarbylene group or C ３ ~C ２０ is a heterohydrocarbylene group, R ３ But hydrogen, C １ ~C ２０ a hydrocarbyl group, or C １ ~C ２０ is a heterohydrocarbyl group, R ４ and R ５ became independent and C １ ~C ２０ Hydrocarbyl group or C １ ~C ２０ heterohydrocarbyl groups, R １ and R ２ optionally joined to form L １２ｒ Forming L １２ｒ But C ３ ~C ２０ Hydrocarbylene group or C ３ ~C ２０ is a heterohydrocarbylene group, R ４ and R ５ optionally joined to form L ４５ Forming L ４５ But C ４ ~C ２０ Hydrocarbylene group or C ４ ~C ２０ is a heterohydrocarbylene group, 32. The method of claim 31 .

33. The n input variables I １ , I ２ , …I ｎ but the following variables: (a) Cr-P distance (Å), (b) Cr-N distance (Å), (c) R-to-R distance on Cr---α-C (Å), (d) P-Cr-N angle (degrees), (e) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to or within bonding distance of said Cr atom; (f) Cr-N-C angle (degrees), (g) distance from the pocket R(Cr-N 1 )·sin(∠Cr-N 1 −P) (Å); (h) Cr---α-C distance (Å), (i) Cr CHELPG (atomic charge), (j) P CHELPG (atomic charge), (k) N CHELPG (atomic charge), (l) Cr-N-CN dihedral angle (degrees), (m) Cr-PNC dihedral angle (degrees), (n) P-Cr-N-C dihedral angle (degrees), (o) P-N-CN dihedral angle (degrees), (p) the C-C-N-C dihedral angle (degrees), or (q) the buried volume percent, defined as the extent to which the first coordination sphere of the Cr metal center is occupied by (P,N) heteroatom ligands, as used in Nat. Chem. 2019, 11(10), 872-879; 32. The method of claim 31 , comprising or selected from any one or more of:

34. any one of the one or more ground state model structures and the plurality of transition state model structures; 【Transformation 8】 and During the ceremony, Each R １ｓ , R ２ｓ , R ５ｓ , R １１ｓ , R １２ｓ , R １３ｓ , and R １４ｓ are independently hydrogen or C １ ~C ２０ is selected from organyl groups, Each L １ｓ , L ３ｓ , and L ４ｓ became independent and C ２ ~C ２０ organylene groups, Any two geminal R １ｓ optionally joined to form L １１ｓ Forming L １１ｓ However, C2 to C ３０ is an organylene group, Any two geminal R ２ｓ optionally joined to form L ２２ｓ Forming L ２２ｓ However, C2 to C ３０ is an organylene group, Any geminal R １１ｓ and R １２ｓ optionally joined to form L １２ｓ Forming L １２ｓ However, C2 to C ３０ is an organylene group, Any geminal R １３ｓ and R １４ｓ optionally joined to form L ３４ｓ Forming L ３４ｓ However, C2 to C ３０ is an organylene group, " ＊ represents any additional bond required in [1] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes, or [2] any of the one or more ground state model structures or any of the plurality of transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes, 25. The method of claim 24.

35. Each R １ｓ , R ２ｓ , R ５ｓ , R １１ｓ , R １２ｓ , R １３ｓ , and R １４ｓ are independently hydrogen, C １ ~C ２０ a hydrocarbyl group, or C １ ~C ２０ heterohydrocarbyl groups, Each L １ｓ , L ３ｓ , and L ４ｓ became independent and C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ heterohydrocarbylene groups; Any two geminal R １ｓ optionally joined to form L １１ｓ Forming L １１ｓ But C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ is a heterohydrocarbylene group, Any two geminal R ２ｓ optionally joined to form L ２２ｓ Forming L ２２ｓ But C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ is a heterohydrocarbylene group, Any geminal R １１ｓ and R １２ｓ optionally joined to form L １２ｓ Forming L １２ｓ But C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ is a heterohydrocarbylene group, Any geminal R １３ｓ and R １４ｓ optionally joined to form L ３４ｓ Forming L ３４ｓ But C ２ ~C ２０ Hydrocarbylene group or C ２ ~C ２０ is a heterohydrocarbylene group, 35. The method of claim 34.

36. The n input variables I １ , I ２ , …I ｎ but the following variables: (a) the first, second, or third Cr-N distance (Å); (b) the first, second, or third Cr-P distance (Å); (c) the first or second Cr-S distance (Å); (d) any one or more N-Cr-N angles (degrees); (e) any one or more P-Cr-P angles (degrees); (f) any one or more S-Cr-S angles (degrees); (g) any one or more S-Cr-N angles (degrees); (h) any one or more N—Cr—P angles (degrees); (i) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to or within bonding distance of said Cr atom; (j) C-Cr-P angle (degrees), (k) C-Cr-S angle (degrees), (l) Cr-N-C angle (degrees), (m) Cr-P-C angle (degrees), (n) Cr-S-C angle (degrees), (o) Cr-P-C angle (degrees), (p) Cr---α-C inter-R distance (Å), (q) distance from the pocket R(Cr-N 1 )·sin(∠Cr-N 1 −P) (Å); (r) Cr---α-C distance (Å), (s) Cr CHELPG (atomic charge), (t) any P CHELPG (atomic charges), (u) any N CHELPG (atomic charges), (v) any chelate Cr-N-C-C dihedral angle (degrees); (w) any chelate Cr-P-C-C dihedral angle (degrees); (x) any chelate Cr-S-C-C dihedral angle (degrees), or (y) buried volume percent, defined as the extent to which the first coordination sphere of the Cr metal center is occupied by (P,N) heteroatom ligands, as used in Nat. Chem. 2019, 11(10), 872-879; 35. The method of claim 34, comprising or selected from any one or more of:

37. The one or more performance parameters associated with the olefin oligomerization reaction are (a) 1-hexene purity, (b) 1-octene purity, (c) 1-hexene:1-octene ratio (C ６ / C ８ (f) total productivity of 1-hexene and 1-octene; (g) trimerization selectivity to 1-hexene; (h) tetramerization selectivity to 1-octene; (i) 1-octene efficiency of the fourth ethylene addition; or any combination thereof.

38. (a) [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ But, GS Ｉ -I, G.S. Ｉ -II, GS Ｉ -III, GS Ｉ -IV, GS Ｉ -V, GS Ｉ -VI, GS Ｉ -VII, or any combination thereof, and [2] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes. Ａ１ , T.S. Ａ２ , ...TS Ａｍ But, TS Ｉ -I, T.S. Ｉ -II, TS Ｉ -III, TS Ｉ -IV, TS Ｉ -V, or any combination thereof; (b) [1] the one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ ,...GSBx is GS Ｔ -I, G.S. Ｔ -II, GS Ｔ -III, GS Ｔ -IV, GS Ｔ -V, GS Ｔ -VI, GS Ｔ [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex, Ｂ１ , T.S. Ｂ２ , ...TSBy, TS Ｔ -I, T.S. Ｔ -II, TS Ｔ -III, TS Ｔ -IV, TS Ｔ -V, or any combination thereof; (c) the performance parameter related to the olefin oligomerization reaction is the 1-hexene productivity, the 1-octene productivity, or the total productivity of 1-hexene and 1-octene of the heteroatom ligand-metal compound complex; 31. The method of claim 30.

39. (a) [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ But, GS Ｉ [2] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , T.S. Ａ２ , ...TS Ａｍ But, TS Ｉ -III and TS Ｉ - IV, (b) [1] the one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ ,...GSBx is GS Ｔ [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ , T.S. Ｂ２ , ...TSBy, TS Ｔ -III and TS Ｔ - IV, (c) the performance parameter associated with the olefin oligomerization reaction is C ６ / C ８ The ratio is 31. The method of claim 30.

40. (a) [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ But, GS Ｉ -VI, GS Ｉ -VIII, G.S. Ｉ -IX, GS Ｉ -X, GS Ｉ -XI, or any combination thereof, and [2] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes. Ａ１ , T.S. Ａ２ , ...TS Ａｍ But, TS Ｉ -III, TS Ｉ -VI, TS Ｉ -VII, TS Ｉ -VIII, TS Ｉ -IX, TS Ｉ -X, TS Ｉ -XI, TS Ｉ -XII, TS Ｉ -XIII, TS Ｉ -XIV, TS Ｉ -XV, or any combination thereof; (b) [1] the one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ , ...GSBx comprises or is independently selected from GST-VI, GST-VIII, GST-IX, GST-X, GST-XI, or any combination thereof, and [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. Ｂ１ , T.S. Ｂ２ , ...TSBy includes or is selected from TST-III, TST-VI, TST-VII, TST-VIII, TST-IX, TST-X, TST-XI, TST-XII, TST-XIII, TST-XIV, TST-XV, or any combination thereof; (c) the performance parameter related to the olefin oligomerization reaction is 1-hexene purity; 31. The method of claim 30.

41. (a) [1] one or more ground state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ But, GS Ｉ -VII, GS Ｉ -XII, GS Ｉ [2] the one or more ground state model structures GS derived from the first target heteroatom ligand-metal compound complex; Ｂ１ ,...GSBx is GS Ｔ -VII, GS Ｔ -XII, GS Ｔ -XIII, or any combination thereof; (b) the performance parameter related to the olefin oligomerization reaction is 1-octene purity; 31. The method of claim 30.

42. (a) [1] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , T.S. Ａ２ , ...TS Ａｍ is the ground state model structure GS Ｉ Addition of the olefin to -VI gives the ground state model structure GS Ｉ and / or [2] a plurality of transition state model structures TS derived from one or more first target heteroatom ligand-metal compound complexes. Ｂ１ , T.S. Ｂ２ , ...TSBy is the ground state model structure GS Ｔ Addition of the olefin to -VI gives the ground state model structure GS Ｔ -VII, or (b) [1] the plurality of transition state model structures TS derived from the first training heteroatom ligand-metal compound complex; Ａ１ , T.S. Ａ２ , ...TS Ａｍ However, the transition state TS Ｉ and / or [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. Ｂ１ , T.S. Ｂ２ , ...TSBy is the transition state TS Ｔ - IV, 31. The method of claim 30.

43. (a) [1] the plurality of transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes; Ａ１ , T.S. Ａ２ , ...TS Ａｍ is the ground state model structure GS Ｉ Transition state and / or ground state model structure GS for β-H abstraction from β-VI to produce 1-hexene Ｉ [0022] [0023] [0024] [0025] [0026] [0027] [0028] [0029] [0030] [0029] [0031] [0029] [0032] [0033] [0029] [0034] [0035] [0036] [0037] [0038] [0039] [ Ｂ１ , T.S. Ｂ２ , ...TSBy is the ground state model structure GS Ｔ Transition state and / or ground state model structure GS for β-H abstraction from β-VI to produce 1-hexene Ｔ -VII by β-H abstraction to produce 1-octene, (b) [1] the plurality of transition state model structures TS derived from the first training heteroatom ligand-metal compound complex; Ａ１ , T.S. Ａ２ , ...TS Ａｍ But, TS Ｉ -III or TS Ｉ and / or [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. Ｂ１ , T.S. Ｂ２ , ...TSBy, TS Ｔ -III or TS Ｔ -including V, 31. The method of claim 30.

44. the one or more ground state model structures GS derived from the one or more first training heteroatom ligand-metal compound complexes; Ａ１ , ...GS Ａｐ and each of the plurality of transition state model structures TS Ａ１ , T.S. Ａ２ , ...TS Ａｍ For each of the n input variables I １ , I ２ , …I ｎ 25. The method of claim 24, wherein the quantitative value assigned to is assigned based on a calculated value, a measured value, or an estimated value, or any combination thereof.

45. said step of forming said second target heteroatom ligand-metal compound complex comprises: (a) one or more n input variables I １ , I ２ , …I ｎ , or I １．１ , I ２．１ , …I ｎ．１ and converting the quantitative value of n to a corresponding n output variables O in any first training heteroatom ligand-metal compound complex comprising a chromium heteroatom ligand moiety independently selected from NPFCrM-1, NPACrM-1, GuCrM-1, GuCrM-2, GuCrM-3, GuCrM-4, GuCrM-5, or HCPACrM-1. １ , O ２ , ...O ｎ , or O １．１ , O ２．１ , ...O ｎ．１ To approach the value of [1] Group R １ , R ２ , L １２ｒ , R ２ａ , R ２ｂ , L １２ , L ２３ , L ２２ , R ３ , R ４ , R ５ , and L ４５ Independently increasing or decreasing the steric volume of one or more of [2] The group R １ , R ２ , L １２ｒ , R ２ａ , R ２ｂ , L １２ , L ２３ , L ２２ , R ３ , R ４ , R ５ , and L ４５ Independently varying one or more of the induced electronic effects of [3] independently increasing or decreasing the degree of saturation in one or more of the organyl or organylene groups; [4] Increasing or decreasing the polarity of the solvent used in the oligomerization of olefins, or [5] any combination thereof; and adjusting by (b) generating a second target heteroatom ligand-metal compound complex for olefin oligomerization, the second target heteroatom ligand comprising the second target heteroatom ligand, based on the at least one adjusted n input variables from step (a); 25. The method of claim 24, comprising:

46. said step of forming said second target heteroatom ligand-metal compound complex comprises: (a) one or more n input variables I １ , I ２ , …I ｎ , or I １．１ , I ２．１ , …I ｎ．１ and calculating the corresponding n output variables O in any first training heteroatom ligand-metal compound complex comprising a chromium heteroatom ligand moiety independently selected from NRNCrM-1, PRPCrM-1, SRSCrM-1, PNPCrM-1, NRNRNCrM-1, PRPRPCrM-1, SRNRSCrM-1, PRNRPCrM-1, or NRPRNCrM-1. １ , O ２ , ...O ｎ , or O １．１ , O ２．１ , ...O ｎ．１ To approach the value of [1] Group R １ｓ , R ２ｓ , R ５ｓ , R １１ｓ , R １２ｓ , R １３ｓ , R １４ｓ , L １ｓ , L ３ｓ , L ４ｓ , L １ｓｒ , L １ｓｒ , L １２ｓｒ , and L ３４ｓｒ Independently increasing or decreasing the steric volume of one or more of [2] The group R １ｓ , R ２ｓ , R ５ｓ , R １１ｓ , R １２ｓ , R １３ｓ , R １４ｓ , L １ｓ , L ３ｓ , L ４ｓ , L １ｓｒ , L １ｓｒ , L １２ｓｒ , and L ３４ｓｒ Independently varying one or more of the induced electronic effects of [3] independently increasing or decreasing the degree of saturation in one or more of the organyl or organylene groups; [4] Increasing or decreasing the polarity of the solvent used in the oligomerization of olefins, or [5] any combination thereof; and adjusting by (b) generating a second target heteroatom ligand-metal compound complex for olefin oligomerization, the second target heteroatom ligand comprising the second target heteroatom ligand, based on the at least one adjusted n input variables from step (a); 25. The method of claim 24, comprising:

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