Machine learning and statistical analysis for catalyst structure prediction and design

Abstract

Disclosed is a transition state model of heteroatomic ligand-metal compound complexes that has been developed for activity, purity, and / or selectivity to selective ethylene oligomerization, and density functional theory calculations for determining reactivity, product purity, and / or selectivity to ethylene trimerization and / or tetramerization of heteroatomic ligand-metal compound complexes. Using reaction basestates and transition states, and / or reaction basestates and transition states in combination with an energy span model, the present disclosure reveals a chromatic ring mechanism, i.e., there are multiple basestates and multiple transition states, which can account for activity, purity, and / or selectivity to selective ethylene oligomerization. Based on the reaction basestates and transition states, and / or reaction basestates and transition states in combination with the energy span model, the methods disclosed herein can be used qualitatively and semi-quantitatively to predict the activity, purity, and / or selectivity of relative heteroatomic ligand-metal compound complexes, and to produce a successful approach for catalyst design and implementation, where new ligands can be successfully identified and validated experimentally.

Description

[0001] Cross-references to related applications

[0002] This application claims priority and benefit to U.S. Provisional Patent Application No. 63 / 037,405, filed June 10, 2020, which is incorporated herein by reference in its entirety. Technical Field

[0003] This disclosure relates to computational methods for developing new catalyst systems, including chromium-based catalyst systems for the selective conversion of ethylene to α-olefins. Background Technology

[0004] Selective ethylene oligomerization yields short-chain linear α-olefins (LAOs) for the manufacture of plasticizers, lubricants, detergents, and linear low-density polyethylene. Chromium-based complexes (e.g., (Cr)-phosphine molecular catalysts) have emerged in forms well-suited for large-scale industrial use. The reactivity of chromium complexes (used herein synonymously with activity) is highly dependent on the correct ligand (e.g., a phosphine ligand) coordinated to Cr. However, there is currently no simple set of empirical parameters or design principles that allow for the reliable prediction of chromium complexes exhibiting high activity, high product purity, and / or high selectivity for ethylene trimerization and / or tetramerization. Furthermore, a general strategy for calculating the design of homogeneous molecular catalysts remains elusive.

[0005] Therefore, new methods are still needed, including novel computational methods for designing and developing ethylene oligomeric chromium complexes with improved activity, improved product purity, and / or improved selectivity for the formation of 1-hexene and / or 1-octene. New computational methods, experimentally verifiable to better design novel chromium-based complexes for selective ethylene oligomerization, particularly those that increase catalyst activity / productivity, product purity, and / or 1-octene selectivity, are also required. Summary of the Invention

[0006] This disclosure provides novel methods for designing and developing ethylene oligomerization catalysts with improved activity / productivity, improved 1-hexene and / or 1-octene selectivity, and / or improved 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 for designing and improving novel heteroatom ligand-metal compound complexes for selective ethylene oligomerization, including increased 1-octene selectivity and other properties. Heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes, such as CrN-phosphinemid (Cr(P,N)) or ((P,N)Cr) catalysts and other catalysts described herein) have been examined and designed using transition state models of activity / productivity, product purity, and / or selectivity calculated by various methods.

[0007] Heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes, such as CrN-phosphineamidine (Cr(P,N)) complexes, and other complexes disclosed herein) can provide high selectivity (approximately 99%) for 1-hexene. When designing novel heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes) with increased activity / yield, increased product purity, and / or greater selectivity for 1-hexene and / or 1-octene, the design process may involve identifying (also referred to as “guiding”) key heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes, such as CrN-phosphineamidine (Cr(P,N)) complexes, and other complexes disclosed herein) that affect the relative energies of the ground and transition states influencing yield, product purity, and / or 1-octene and / or 1-hexene selectivity, using a “training” (also “guiding”) approach. The same design process can also be used to improve the selectivity of trimerization catalytic cycles for 1-hexene (also known as trimerization cycle selectivity for 1-hexene), the selectivity of tetramerization catalytic cycles for 1-octene, and / or the efficiency of 1-octene in the fourth ethylene addition. These key structural or electronic features can be used as input variables for developing computational designs that examine their relative importance in terms of their influence on the relative energies of the ground and transition states, and thus on the overall activity / productivity, purity, and / or selectivity of the oligomerization process. Based on such computational designs, "target" heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes, such as Cr(P,N) complexes, and other complexes disclosed herein) can be identified according to desired adjustments to their structural or electronic features, and these target complexes can be synthesized and verified experimentally. Based on these results, next-generation target complexes can be identified using computational redesign or iteration, which can also be verified experimentally and further tested and redesigned. In this way, the performance of heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes) can be predicted and improved.

[0008] On one hand, for example, transition state models for heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes, such as CrN-phosphinemidine complexes and other complexes disclosed herein) have been developed for activity / productivity, product purity, and / or selectivity, and complex reactivity of activity / productivity, product purity, and / or ethylene trimerization and tetramerization can be solved using density functional theory calculations. Using ground state and transition state models and / or combining them with energy span models, this disclosure reveals mechanisms including metal ring intermediates that can be used to predict the activity / productivity, product purity, and / or selectivity of heteroatom ligand-metal compound complexes. For example, in a non-limiting aspect, heteroatom ligand-chromium compound complexes can utilize high-spin Cr...I / III A chromocyclic mechanism, involving multiple CrI ethylene coordination ground states and multiple transition states, can be used to predict and / or estimate the activity / productivity, product purity, and / or selectivity of heteroatom ligand-metal compound complexes. Based on the calculated energy landscape, the calculated activity / productivity, product purity, and / or selectivity of heteroatom ligand-metal compound complexes can be correlated with experimental values, and this correlation can be used to predict the activity / productivity, product purity, and / or selectivity of new heteroatom ligand-metal compound complexes. This analysis can therefore calculate and compare the activity, productivity, product purity, and / or selectivity of other heteroatom ligand-metal compound complexes. Based on the catalytic energy span of heteroatom ligand-metal compound complexes, the calculations disclosed herein can qualitatively and semi-quantitatively replicate the relative activity / productivity, product / purity, and / or selectivity of heteroatom ligand-chromium compound complexes, and guide us to a successful process for the design and implementation of heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes), where new heteroatom ligands can be successfully identified and experimentally validated.

[0009] Furthermore, this disclosure provides a method for designing heteroatom ligand-metal compound complexes for olefin oligomerization, which identifies and examines numerous possible ground and transition states during the oligomerization process, including the ground states that transcend different transition states to produce the desired oligomeric products (e.g., olefin trimers and / or olefin tetramers compared to other olefin oligomers). This method allows for the identification of key synaptic and electronic characteristics of the identified ground and transition states that affect activity / productivity, product purity, and / or selectivity, and provides information on how to tune these characteristics in next-generation designs to enhance activity / productivity, product purity, and selectivity.

[0010] On the one hand, heteroatom ligand-metal compound complexes can have the general formula [(HetLig)CrX]. q L r ] 3-q (A) A heteroatom ligand-chromium compound complex, wherein: HetLig represents a trained heteroatom ligand whose electronic and / or structural properties can be examined and adjusted to alter the ligand's electronic and / or structural properties; X is an anionic ligand, and q is an integer; L is a neutral ligand; and r is an integer; wherein any two or more of the X and L ligands can connect to form a polydentate ligand. This disclosure examines the detailed characterization of heteroatom ligands and their complexes with metal compounds (e.g., chromium compounds) and how such characterization affects the energy dynamics of the ground and transition states.

[0011] Therefore, in one aspect, this disclosure provides a method for designing heteroatom ligand-metal compound complexes for olefin oligomerization, the method comprising:

[0012] (a) Select n input variables I 1 I 2 ...I n (n is an integer), each input variable corresponds to one or more ground state model structures GS. A1 ...GS Ap (p is an integer) and multiple transition state model structures TS associated with the one or more ground state model structures. A1 TS A2 ...TS Am (m is an integer) structural or electronic properties

[0013] The one or more ground state model structures GS A1 ...GS Ap Each of the multiple transition state model structures TS A1 TS A2 ...TS Am Each of them is derived from one or more first-trained heteroatom ligand-metal compound complexes, and each complex contains a first-trained heteroatom ligand;

[0014] (b) For the ground state model structure GS A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am Each of the n input variables I represents a given set of n input variables. 1 I 2 ...I n Allocate quantitative values;

[0015] (c) The ground state model structure GS is determined by at least one processor of the device. A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am The relative energy of each of them;

[0016] (d) Based on the input variables I for every n... 1 I 2 ...I n The quantitative value and the ground state model structure GS A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am The relative energies of each of them are interconnected, generating a machine learning model;

[0017] (e) Based on the machine learning model, identify the n input variables I. 1 I 2 ...I n One or more input variables related to the following: [1] the ground state model structure GS A1 ...GS Ap One of the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between at least one of them [ΔG(TS-GS) or ΔΔG(TS-GS)] or [2] the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between any two or more of them [ΔG(TS-TS) or ΔΔG(TS-TS)];

[0018] (f) Based on the one or more n input variables I identified from step (e) 1 I 2 ...I n Generate a first target heteroatom ligand-metal compound complex for olefin oligomerization and comprising a first target heteroatom ligand, wherein the first target heteroatom ligand-metal compound complex is characterized by n output variables O 1 O 2 ...O n Each output variable has a corresponding ground state model structure GS. B1 ...GS Bx (x is an integer) or multiple transition state model structures TS associated with one or more ground state model structures. B1 TS B2 ...TS By A quantitative value of any one of the structural or electronic properties (y is an integer).

[0019] The one or more ground state model structures GS B1 ...GS Bx Each of the multiple transition state model structures TS B1 TS B2 ...TS By Each of them is derived from the first target heteroatom ligand-metal compound complex, and each complex contains the first target heteroatom ligand;

[0020] (g) For the one or more first training heteroatom ligand-metal compound complexes and the first target heteroatom ligand-metal compound complexes, identify one or more performance parameters related to the olefin oligomerization reaction and the values ​​of the performance parameters; and

[0021] (h) Using the n output variables O of the first target heteroatom ligand-metal compound complex 1 O 2 ...O n The quantitative value is derived from n new input variables I for olefin oligomerization and one or more second-trained heteroatom ligand-metal compound complexes containing second-trained heteroatom ligands. 1.1 I 2.1 ...I n.1 Given an input dataset, repeat steps (a)-(f) once or more, and evaluate the input dataset against a machine learning model to generate a second target heteroatom ligand-metal compound complex containing a second target heteroatom ligand, wherein the second target heteroatom ligand-metal compound complex is characterized by new n output variables O 1.1 O 2.1 ...O n.1 The output dataset contains quantitative values ​​and performance parameter values ​​for one or more second-target heteroatom ligand-metal compound complexes.

[0022] In this respect, in step (b), for the ground state model structure GS A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am Each of the n input variables I represents a given set of n input variables. 1 I 2 ...I n Quantitative values ​​are assigned, which can be independently assigned either original or normalized values. Also in this respect, in step (c), (c) the ground-state model structure GS is determined by at least one processor of the device. A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am The relative energy of each of them, these determined relative energies can be independently the relative energy of the possible conformational ensembles of the ground state model structure and the transition state model structure or a specific conformation.

[0023] Furthermore in this respect, in step (d), the machine learning model of step (e) can convert every n input variables I 1 I 2 ...I n The quantitative value and the ground state model structure GS A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am The relative energies of each of the n input variables are interconnected. In this way, for every n input variables I... 1 I 2 ...I n Values ​​and ground state model structure GS A1 ...GS Ap There may be a relationship between the relative energies, and for every n input variables I 1 I 2 ...I n Values ​​and Transition State Model Structure TS A1 TS 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 them are in Figure 1 The example is shown below.

[0024] Furthermore in this respect, in step (e), the relationship in step (d) allows for the input variables I of n. 1 I 2 ...I n One or more of them are mapped to the following: [1] the ground state model structure GS A1 ...GS Ap One of the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between at least one of them [ΔG(TS-GS) or ΔΔG(TS-GS)] or [2] the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between any two or more of the n input variables I [ΔG(TS-TS) or ΔΔG(TS-TS)]. Specifically, the n input variables I are identified. 1 I 2 ...I nOne or more input variables related to [1]ΔG(TS-GS) or ΔΔG(TS-GS) or [2]ΔG(TS-TS) or ΔΔG(TS-TS), whose energy differences can be based on Boltzmann ensemble ΔG or ΔΔG values.

[0025] Further, in this regard, the machine learning models in steps (d), (e), and (h) may include one or more neural networks. These machine learning models can be iteratively applied to identify and tune key structural or electronic features of heteroatom ligand-metal compound complexes that affect the relative energies of the ground and transition states for activity / productivity, selectivity (yield of 1-octene versus 1-hexene), and product purity (1-hexene versus other C6 products and / or 1-octene versus other C8 products). These key structural or electronic features can be used as n input variables I of the machine learning model. 1 I 2 ...I n This allows for the training of machine learning models to examine the relative importance of structural or electronic features in influencing the relative energies of the ground and transition states, and thus the overall activity / productivity, product purity, and selectivity of the oligomerization process. In this way, machine learning models can be trained to assess the impact of structural or electronic features on the relative energies of the ground and transition states, and thus 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 based on desired adjustments to their structural or electronic features, and these target complexes can be synthesized and experimentally verified. Based on these results, computational redesign or iteration can be used to identify next-generation target complexes, which can also be experimentally verified and further tested and redesigned using the machine learning models.

[0026] Further, in this respect, step (f) can use the mapping generated in step (e) as input to generate an output comprising a first target heteroatom ligand-metal compound complex, the complex being used for olefin oligomerization and containing the first target heteroatom ligand, wherein the first target heteroatom ligand-metal compound complex is characterized by n output variables O 1 O 2 ...O n Each output variable has a corresponding ground state model structure GS. B1 ...GS Bx (x is an integer) or multiple transition state model structures TS associated with one or more ground state model structures. B1 TS B2 ...TSB A quantitative value for any one of the structural or electronic properties of y (where y is an integer). The one or more ground-state model structures GS B1 ...GS Bx Each of the multiple transition state model structures TS B1 TS B2 ...TS By Each of these is generated from a first target heteroatom ligand-metal compound complex, and each complex contains the first target heteroatom ligand. In this way, n output variables O 1 O 2 ...O n The new n input variables I are reused as a machine learning model 1.1 I 2.1 ...I n.1 The machine learning model can evaluate the corresponding effects of input variables on the relative energies of the ground state and the transition state.

[0027] Further in this regard, step (h) may involve using the n output variables O of the first target heteroatom ligand-metal compound complex. 1 O 2 ...O n The quantitative value is used as the new n input variables I 1.1 I 2.1 ...I n.1 The input dataset is iterated and steps (a)-(f) are repeated once or more, with the new n input variables I... 1.1 I 2.1 ...I n.1 Derived from one or more second-trained heteroatom ligand-metal compound complexes used for olefin oligomerization and containing a second training heteroatom ligand, the input dataset is fed into the machine learning model to generate a second-target heteroatom ligand-metal compound complex containing a second target heteroatom ligand, wherein the second-target heteroatom ligand-metal compound complex is characterized by new n output variables O 1.1 O 2.1 ...O n.1 The output dataset contains quantitative values ​​and performance parameter values ​​for one or more second target heteroatom ligand-metal compound complexes. In this way, the machine learning model can continue to learn which structural or electronic features of the heteroatom ligand-metal compound complex affect the relative energies of the ground and transition states, and the degree of significant influence, in order to identify the target heteroatom ligand-metal compound complex.

[0028] Furthermore, the disclosed method may also include the following steps in this regard:

[0029] (i)[1] Synthesize the first target heteroatom ligand and / or the second target heteroatom ligand; or [2] Synthesize the first target heteroatom ligand and / or the second target heteroatom ligand, and then synthesize the first target heteroatom ligand-metal compound complex or the second target heteroatom ligand-metal compound complex.

[0030] Similarly, in this respect, the disclosed method may further include the following steps:

[0031] (j) The olefin oligomerization reaction is carried out 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.

[0032] These and other embodiments and aspects of processes, methods, and compositions including catalyst compositions are more fully described in the detailed description and claims, as well as in further disclosures (such as the examples provided herein). Attached Figure Description

[0033] Figure 1 This describes some geometric input variables used in various aspects of the method according to this disclosure.

[0034] Figure 2A , Figure 2B and Figure 2C The following describes the descriptors extracted for machine learning analysis. Figure 2A It provides geometry descriptors and static charge. Figure 2B The definition of the percentage of buried volume is explained. Figure 2C It demonstrates the definition of the distance outside the bag.

[0035] Figure 3 The reaction scheme for 1-hexene switching frequency is illustrated, showing various ground and transition states, and the transition state energy barrier that can contribute to the 1-hexene switching frequency and thus to productivity is explained.

[0036] Figure 4 The ground state and transition state are described, and in addition to the ground state and transition state, the transition state energy barrier is also described, as well as... Figure 3 The transition state energy barrier described in the figure may be what is needed for a 1-octene switching frequency reaction scheme starting from GS-VI, which can contribute to the 1-octene switching frequency and thus to the activity / productivity.

[0037] Figure 5AThis disclosure illustrates one aspect of the catalytic cycling pathway through which 1-hexene and / or 1-octene can be obtained from a common ground state and can be used to calculate C6 / C8 selectivity.

[0038] Figure 5B Another aspect of this disclosure illustrates a catalytic cycling pathway through which 1-hexene and / or 1-octene can propagate via trimerization and / or tetramerization catalytic cycles to produce branched decene, branched dodecene, and / or branched tetradecene.

[0039] Figure 5C Further illustrating another aspect of this disclosure, a catalytic cycling pathway is shown through which 1-hexene and / or 1-octene can be propagated via trimerization and / or tetramerization catalytic cycles to produce branched decene, branched dodecene, and / or branched tetradecene.

[0040] Figure 6 This explains the pathways through which 1-hexene can be formed and the pathways through which six-carbon impurities can appear in the formation of 1-hexene.

[0041] Figure 7 This demonstrates the energy difference of the transition state (TS) ensemble, which can control the pathway to obtain 1-hexene and other C6 compounds, which may be impurities in the isolated 1-hexene product.

[0042] Figure 8 This section describes a comparison of the ligands used in the heteroatom ligand-chromium compound complex ethylene trimer in the experimental report and their productivity in g 1-C6 / g Cr·h. The mass percentage of 1-hexene in the total mass of the C6 product is given in parentheses.

[0043] Figure 9A A simplified Gibbs free energy landscape is provided for the trimerization of ethylene using two different heteroatom ligands in heteroatom ligand-chromium compound complexes (i.e., (P,N)Cr1a and (P,N,P)Cr8a), where the ligands are denoted by HetLig. Intermediates GS-I and GS-II of catalyst 1a are six-spin, and all other intermediates and transition states are four-spin. The numbers indicated in parentheses represent the relative contribution of the structure to the transition frequency of the ground or transition state with respect to the heteroatom ligand-chromium compound complex.

[0044] Figure 9B The ground and transition Gibbs free energies, in kcal / mol, of the ethylene trimerization catalytic cycle using heteroatom ligand-chromium compound complexes with ligands 2-7 are presented.

[0045] Figure 10 The key intermediates and transition states of catalysts 1a and 8a are illustrated in 3D. Some atoms have been removed for clarity.

[0046] Figure 11 The Gibbs free energy surface for ethylene trimerization using catalyst 1a is illustrated. The solid line surface is the simplified Gibbs free energy surface for ethylene trimerization using catalyst 1a at an ethylene pressure of 50 bar with M06-L, and the dashed line surface is the Gibbs free energy landscape of ωB97X-D (kcal / mol).

[0047] Figure 12 A plot is shown comparing the natural logarithm of the experimental productivity values ​​(g 1-C6 / g Cr·h) corrected only for 1-hexene with the natural logarithm of the calculated 1-C6 productivity values. 8a productivity is rated as the natural logarithm of 1.

[0048] Figure 13A This paper outlines the selective ethylene oligomerization catalyzed by heteroatom ligand-chromium compound complexes targeting 1-hexene and 1-octene, using heteroatom ligand-chromium compound complexes with phosphine and imine ligand coordination, i.e., "Cr(P,N)", typically activated by a modified methylaluminoxane (MMAO) pre-catalyst complex.

[0049] Figure 13B The transition state selectivity model used in this disclosure is described, wherein a computational check examines the cationic high-spin transition state TS-III that produces 1-hexene and the cationic high-spin transition state TS-IV that produces 1-octene to develop a linear correlation model between DFT calculations and experimental 1-hexene:1-octene ratios.

[0050] Figure 13C The workflow of this disclosure is illustrated, which combines transition states and machine learning 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 and then used for the virtual design of novel catalyst ligands.

[0051] Figure 14 This paper outlines 105 unique heteroatom ligand-chromium compound complexes with phosphine and imine ligand coordination, i.e., “Cr(P,N)” ligands, in transition state training or guidance datasets. These complexes have a variety of different functional groups but retain the phosphine and imine or imine-like ligand coordination for developing DFT transition state models.

[0052] Figure 15 The figure illustrates the root mean square error (RMSE) of a machine learning regression algorithm that uses 14 atomic and molecular features to quantitatively predict the energy difference between TS-III and TS-IV. In this figure, RF = Random Forest, LASSO = Minimum Absolute Value Convergence and Selection Operator, GPR = Gaussian Process Regression, and SVR = Support Vector Regression.

[0053] Figure 16A Linear regressions of selectivity predicted by the DFT selectivity model (x-axis) and the optimized random forest (RF) model (y-axis) are shown. Negative values ​​correspond to high 1-hexene selectivity, and positive values ​​correspond to high 1-octene selectivity.

[0054] Figure 16B Linear regressions of 1-octene selectivity predicted by the DFT selectivity model (circle) and the optimized random forest (RF) model (triangle) are provided compared with experimental values.

[0055] Figure 17 The machine learning average prediction selectivity (red) was compared with the DFT computational selectivity.

[0056] Figure 18 This illustrates the importance of normalized features determined from the random forest model using 95% confidence intervals (red bars). Dist Poc is the distance outside the bag; Vol Bur is the percentage of burial volume; other parameters include... Figure 1 and Figure 2A As shown.

[0057] Figure 19A The structures of previous multi-generation (P, N) ligands and newly proposed ligands (generation 3) are illustrated based on features identified using machine learning. The 1-hexene:1-octene selectivity (predicted) is given below each structure.

[0058] Figure 19B The 1-octene selectivity of previous heteroatom ligand-chromium compound complexes with phosphine and imine ligand coordination, namely multigenerational "Cr(P,N)" ligands and new generation heteroatom ligands developed in this disclosure, was plotted.

[0059] Figure 20 Competitive and selectivity-determining reactive coordination pathways for the production of hexene and octene are described, including general N... 2 -Ophosphine-amidinium-cycloheptane complexes CrCH1 and CrCH2, and general N 2 -Ophosphine-based amidine chromium salt complex hexene transition state TS C6, and general N 2 -Oxyphosphine-based amidine chromium salt complex octene transition state TS C8.

[0060] Figure 21A This explains the deprotonated NH N 2 -Oxyphosphine-amidinium ligand and Cr I / IIIThe Gibbs free energy landscape of the total neutral Cr catalyst complexes in the cycle is shown, with energies expressed in kcal / mol. The ground states GS-I and GS-II possess six-fold spin states as lower energies, and all other ground and transition states possess four-fold spin states as the lowest energies.

[0061] Figure 21B The deprotonated NH N was shown 2 -Oxyphosphine-amidinium ligand and Cr II / IV The Gibbs free energy landscape of the total cation Cr complex in the cycle, with energies expressed in kcal / mol. The 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.

[0062] Figure 22 This illustrates the Gibbs free energy landscape (kcal / mol) of the N-dimethylaluminum substitution model, particularly with 1c-AIMe2 catalysts and cation Cr. I / III The Gibbs free energy surface of the reaction channel. The ground states GS-I and GS-II have six-spin states as the lowest energy, and all other ground and transition states have four-spin states as the lowest energy.

[0063] Figure 23 The relative energies (in kcal / mol) of all ethylene coordination structures and alternative mechanical pathways involving coordinated ethylene are presented.

[0064] Figure 24 The enthalpy, Gibbs free energy, and entropy-scaled Gibbs free energy surface (ΔG) from the ground state GS-II to GX-VI were compared involving transition states TS-I and TS-II. S，corr ).

[0065] Figure 25 The ωB97X-D Gibbs free energy surface, which is a ethylene pressure correction for the calculated Gibbs free energy surface of 1a, is described, with the kinetic experiment conducted at high ethylene pressure (50 bar).

[0066] Figure 26 Describe the Gibbs free energy level (energy in kcal / mol) of the dissociated amine ligand 8c. The ground states GS-I and GS-II have six-spin states as the lowest energy, and all other ground and transition states have four-spin states as the lowest energy.

[0067] Figure 27Spin crossing is explained, and it has been confirmed that spin crossing provides a lower energy pathway from the bis(ethylene) coordinated Cr ground state GS-II (lowest energy six-fold spin state) to the transition state TS-I, where the spin state is shown in parentheses (energy in kcal / mol).

[0068] Figure 28A The calculated free energy landscape (energy in kcal / mol) of “truncation” model 1b is depicted.

[0069] Figure 28B The calculated free energy landscape (energy in kcal / mol) of the “truncation” model 8b is depicted.

[0070] Figures 29A to 29F The Gibbs free energy levels of chromium complexes containing ligands 2-7 at 298 K and 1 atm are shown, and their solvents are listed in Table S1. Therefore, Figure 29A The surface is a ligand 2 complex; Figure 29B The surface is a ligand 3 complex; Figure 29C The surface is a ligand 4 complex; Figure 29D The surface is a ligand 5 complex; Figure 29E The surface is a ligand 6 complex; and Figure 29F The surface is a ligand 7 complex.

[0071] Figure 30 The energy landscape of M06L for catalyst 1a is shown. The free energy barrier of 6–15 kcal / mol is consistent with the experimental reaction temperature.

[0072] Figure 31 Possible conformations of transition states TS-III and TS-IV for exemplary heteroatom ligand-chromium compound complexes are depicted, namely conformational changes that produce unique transition state geometries.

[0073] Figure 32 The 3-D structures of 20 lowest transition state conformations of exemplary heteroatom ligand-chromium compound complexes in the TS-III ensemble are described, with relative free energies in kcal / mol.

[0074] Figure 33 The 3-D structures of 20 lowest transition state conformations of exemplary heteroatom ligand-chromium compound complexes in the TS-IV ensemble are described, with relative free energies in kcal / mol.

[0075] Figure 34 Linear correlation plots using Boltzmann distributions are provided, including an ensemble of all calculated transition states using the ligands shown for TS-III and TS-IV.

[0076] Figure 35 A schematic diagram illustrates the machine learning model used to generate target heteroatom ligand-metal compound complexes. Detailed Implementation

[0077] Furthermore, this 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). These methods include approaches focusing on activity / productivity, increasing the proportion of 1-octene or 1-hexene in the product, and / or increasing the 1-olefin content in C6 and / or C8 oligomer products. The methods also include approaches focusing on reducing the proportion of byproducts generated. Density functional theory (DFT) calculations have been found to be useful for resolving activity / productivity, product purity, and / or selectivity for selective ethylene oligomerization using a heteroatom ligand-metal compound complex transition state model. This aspect of the disclosure demonstrates the use of ground and transition states and / or the use of ground and transition states combined with energy span models, which allows for 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.

[0078] In one aspect, it is also demonstrated here that combining machine learning computational methods with quantum mechanical transition state models can identify specific design features for selective olefin oligomerization using heteroatom ligand-metal compound complexes. Useful general strategies for virtual catalyst design or improvement have not yet been developed, and it is difficult to identify simple chemical features controlling ethylene oligomerization catalysis where small energy differences can have a significant impact. In another aspect, this disclosure provides the development of density functional theory (DFT) transition state models combined with a heteroatom ligand-metal compound complex design workflow that integrates quantum mechanical transition state modeling with machine learning to reveal specific heteroatom ligand-chromium compound complex design features aimed at producing 1-hexene and / or 1-octene.

[0079] definition

[0080] To more clearly define the terms used herein, the following definitions are provided, and unless otherwise specified or required by context, these definitions apply throughout this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Chemical Terminology Compendium, 2nd Edition (1997) may be applied, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any technical solution to which the definition is applied ambiguous or invalid. If any definition or usage provided in any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0081] Transitional terms or phrases relating to claims, the transitional term "comprising," synonymous with "comprising," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consisting substantially of" limits the scope of the claim to the specified materials or steps, and those that do not materially affect one or more essential and novel features of the claimed invention. Claims "consisting substantially of" fall between closed claims drafted in "consisting of" format and fully open claims drafted in "comprising." Unless stated to the contrary, describing a compound or composition as "consisting substantially of" should not be construed as "comprising," but rather is intended to describe the listed components, including materials that do not significantly alter the composition or method to which the term is applied. For example, a raw material substantially composed of material A may include impurities typically present in commercially produced or commercially available samples of the compound or composition. When a claim contains different features and / or feature categories (e.g., method steps, raw material features, and / or product features, and other possibilities), the transitional terms "comprising," "substantially consisting of," and "consisting of" apply only to the feature category used, and may have different transitional terms or phrases used in the claim with different features. For example, a method may include several listed steps (and other unlisted steps), but prepares a catalyst system using a catalyst composition consisting of specific steps, but utilizing a catalyst system containing listed components and other unlisted components. While compositions, processes, and calculation methods are described with regard to "comprising" individual components or steps, the compositions, processes, and calculation methods may also be "substantially consisting of" individual components and steps or "consisting of" individual components and steps.

[0082] Unless otherwise expressly indicated, the terms “a”, “an”, and “the” are intended to include multiple alternatives, such as at least one alternative. For example, unless otherwise specified, the disclosure of “organoaluminum compound” is intended to cover one organoaluminum compound, or a mixture or combination of more than one organoaluminum compound.

[0083] For any particular compound disclosed herein, unless otherwise indicated, the general structure or name presented is also intended to include all structural isomers, conformational isomers, and stereoisomers that can be produced by a particular set of substituents. Therefore, unless explicitly stated otherwise, compounds generally referred to include all structural isomers; for example, pentane generally refers to n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while butyl generally refers to n-butyl, sec-butyl, isobutyl, and tert-butyl. Additionally, when the context permits or requires, the general structure or name referred to covers all enantiomers, diastereomers, and other optical isomers (whether in enantiomeric or racemic form), as well as mixtures of stereoisomers. For any particular formula or name presented, any general formula or name presented also includes all conformational isomers, regio isomers, and stereoisomers that can be produced by a particular set of substituents.

[0084] Unless otherwise specified, any carbon-containing group without a specified number of carbon atoms may, in accordance with appropriate chemical practice, 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 these values. For example, unless otherwise specified or unless the context requires otherwise, any carbon-containing group may 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. On the one hand, the context may require additional scope or limitations; for example, when the subject matter contains an aryl or alkenyl group, the lower limits for carbon in these subject matter groups are six carbon atoms and two carbon atoms, respectively. Furthermore, other identifiers or qualifying terms may be used to indicate the presence or absence of a specific substituent, a specific region chemistry and / or stereochemistry, or the presence or absence of a branched basic structure or main chain, etc.

[0085] This document discloses various numerical ranges. When an applicant discloses or claims protection for any type of range, unless otherwise specified, the applicant intends to individually disclose or claim protection for every possible number that such range can reasonably include, including the endpoints of the range and any subranges and combinations thereof included therein. For example, by disclosing that the key angle can be from 90° to 100°, the applicant intends to individually list 90°, 91°, 92°, 93°, 94°, 95°, 96°, 99°, 98°, 99°, and 100°, including any subranges and combinations thereof covered therein, and these methods of describing such ranges are interchangeable. Furthermore, all numerical endpoints of the ranges disclosed herein are approximate unless excluded by attached conditions. As a representative example, if the applicant states that one or more steps in the methods disclosed herein can be performed at temperatures ranging from 10°C to 75°C, then this range should be interpreted as including temperatures ranging from “about” 10°C to “about” 75°C.

[0086] Values ​​or ranges herein may be expressed as “about”, from “about” a specific value, and / or to “about” another specific value. When expressing such values ​​or ranges, other disclosed embodiments include the enumerated specific values, from one specific value and / or to another. Similarly, when a value is expressed as an approximation using the antecedent “about,” it should be understood that the specific value forms another embodiment. It should also be understood that numerous values ​​are disclosed herein, and each value, in addition to being stated itself, is also disclosed herein as “about” the specific value. On the other hand, the use of the term “about” means ±15% of the stated value, ±10% of the stated value, ±5% of the stated value, or ±3% of the stated value.

[0087] Therefore, if, for any reason, the applicant chooses to claim protection for a measure less than the full scope of the disclosure, such as considering references the applicant might not have been aware of at the time of filing, the applicant reserves the right to specify or exclude any individual member of any such numerical or range group, including any subranges or combinations of subranges within said group, which can be claimed by scope or in any similar manner. Furthermore, if, for any reason, the applicant chooses to claim protection for a measure less than the full scope of the disclosure, such as considering references or prior disclosures the applicant might not have been aware of at the time of filing, the applicant reserves the right to specify or exclude any individual substituent, analogue, compound, ligand, structure, or group thereof, or any member of the claimed group.

[0088] The term “substituted” when used to describe a group, such as when referring to a substituted analogue of a particular group, is intended to describe any non-hydrogen portion that formally replaces hydrogen in said group, and is not intended to be limiting. One or more groups may also be referred to herein as “unsubstituted,” or equivalent terms such as “non-substituted” refer to the original group in which the non-hydrogen portion does not replace hydrogen in said group. Unless otherwise specified, the term “substituted” is not intended to be limiting and includes inorganic or organic substituents as understood by one of ordinary skill in the art.

[0089] Specific chemical groups can be designated based on the atom bonded to a metal or to another chemical moiety as a substituent, such as "oxygen-bonded groups," also known as "oxygen groups." For example, oxygen-bonded groups include substances such as alkyloxy groups (-OR, where R is a hydrocarbon group, also known as alkyloxy groups), alkoxy groups (-OR, where R is an alkyl group), aryloxy groups (-OAr, where Ar is an aryl group), or their substituted analogs, which act as ligands or substituents at the designated position. Therefore, alkoxy and aryloxy groups are each subgenus of alkyloxy (alkyloxy) groups. A similar definition applies to chemical groups that can be designated based on the atom bonded to a metal or to another chemical moiety as a substituent, where the free valence is located on a heteroatom (non-carbon atom), such as "sulfur groups," "nitrogen groups," "phosphorus groups," "arsenic groups," "silicon groups," "germanium groups," "tin groups," "lead groups," "boron groups," "aluminum groups," etc.

[0090] A chemical “group” can also be described according to how the group is formally derived from a reference or “parent” compound, for example by formally removing the number of hydrogen atoms from the parent compound to produce the group, even if the group is not literally synthesized in this way. These groups can be used as substituents or coordinated or bonded to metal atoms. For example, an “alkyl” can be formally derived by removing one hydrogen atom from an alkane, while an “alkyldiyl” (also called an “alkylene group”) can be formally derived by removing two hydrogen atoms from an alkane. Furthermore, the more general term can be used to include various groups formally derived by removing any number (“one or more”) of hydrogen atoms from a parent compound, which in this example can be described as an “alkane group”, which includes “alkyl”, “alkyldiyl”, and the material has three or more hydrogen atoms that need to be removed from the alkane as appropriate. Substituents, ligands, or other chemical motifs may constitute a public indication that a particular “group” follows known rules of chemical structure and bonding when the group is used as described. Unless otherwise specified or required by the context, when a group is described as “derived from,” “from,” “formed by,” or “made of,” such terms are used in a formal sense and are not intended to reflect any specific synthetic method or procedure.

[0091] The term "organogroup" is used herein according to the definition specified by IUPAC: an organic substituent having a free valence on a carbon atom, regardless of functional type. Similarly, "suborganogroup" refers to an organic group derived by removing two hydrogen atoms from an organic compound, regardless of functional type, where the two hydrogen atoms come from one carbon atom, or one hydrogen atom comes from each of two different carbon atoms. "Organic group" is a generalized group formed by removing one or more hydrogen atoms from a carbon atom of an organic compound. Therefore, "organogroup," "suborganogroup," and "organic group" can contain organic functional groups and / or atoms other than carbon and hydrogen; that is, organic groups that may contain functional groups and / or atoms in addition to 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, and phosphine, etc. On one hand, the hydrogen atom removed to form an "organic group," "suborganic group," or "organic group" can be attached to a carbon atom belonging to a functional group, such as acyl (-C(O)R), formyl (-C(O)H), carboxyl (-C(O)OH), alkyloxycarbonyl (-C(O)OR), cyano (-C=N), carbamoyl (-C(O)NH2), N-alkylcarbamoyl (-C(O)NHR), or N,N′-dialkylcarbamoyl (-C(O)NR2), and other possible functional groups. On the other hand, the hydrogen atom removed to form an "organic group," "suborganic group," or "organic group" can be attached to a carbon atom that does not belong to and is far from a functional group, such as -CH2C(O)CH3, -CH2NR2, etc. The "organic group," "suborganic group," or "organic group" can be aliphatic, including cyclic or acyclic, or can be aromatic. The terms "organogroup," "suborganogroup," and "organic group" also encompass heteroatom-containing rings, heteroatom-containing ring systems, heteroaromatic rings, and heteroaromatic ring systems. Unless otherwise specified, "organogroup," "suborganogroup," and "organic group" can be straight-chain or branched. Finally, note that the definitions of "organogroup," "suborganogroup," or "organic group" respectively include "hydrocarbon group," "hydrocarbon group," and "hydrocarbon group," and respectively include "alkyl group," "alkylene group," and "alkane group" as members (as well as other groups known to those skilled in the art). When bonded to a transition metal, "organogroup," "suborganogroup," or "organic group" can be determined according to the usual η x The (η-x) nomenclature is further described, where x is an integer corresponding to the number of atoms coordinated with or expected to be coordinated with a transition metal, for example, according to the 18-electron rule.

[0092] The formamidinium group has a general formula structure The nitrogen atom that forms a double bond with the central carbon atom within the formamidinium group is called N. 1Nitrogen that forms a single bond with the central carbon atom is called N. 2 Nitrogen. Similarly, attached to N 1 and N 2 The groups on the nitrogen atom are called N. 1 Groups and N 2 Group. N 2 The -oxophosphine-formamidinium group has a general formula structure. In N 2 Within the -oxophosphine-formamidinium group, N 1 and N 2 Nitrogen atom and N 1 and N 2 The group has the same meaning as described for the formamidin group. Therefore, N 2 -Ophosphine-formamidinium group has an attachment to N 2 The phosphine group on the nitrogen atom. The amidine group has the general formula... The group consisting of nitrogen atoms that form a double bond with the central carbon atom within the amidine group is called N. 1 Nitrogen that forms a single bond with the central carbon atom is called N. 2 Nitrogen. Similarly, attached to N 1 and N 2 The groups on the nitrogen atom are called N. 1 Groups and N 2 Group. N 2 The -oxophosphinemidine group has the general formula structure. In N 2 Within the -oxophosphinemidine 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. Therefore, N 2 -Oxyphosphinemidine group has an attachment to N 2 The phosphine group on the nitrogen atom. In the amidine group and N... 2 Within the α-phosphinemidine group, the carbon atom between the two nitrogen atoms is the central carbon atom, and any substituent attached to it is called the central carbon group.

[0093] Guanidinyl is a group with a general formula structure The group. Within the guanidine nucleus, the nitrogen atom that forms a double bond with the central carbon atom is called N. 1 Nitrogen atoms that form a single bond with the central carbon atom are called N atoms. 2 Nitrogen and N 3 Nitrogen. Similarly, attached to N 1 N 2 and N 3 The groups on the nitrogen atom are called N. 1 Group, N 2 Groups and N 3 Group. N2 The -oxophosphine guanidine group has a general formula structure. In N 2 The nitrogen in the α-oxophosphine guanidine group that forms a double bond with the central carbon atom of the guanidine nucleus is called N. 1 Nitrogen, the nitrogen atom that forms a single bond with the central carbon atom of the guanidine nucleus and a bond with the phosphorus atom of the phosphine group, is called N. 2 Nitrogen, and the remaining nitrogen atoms that form single bonds with the central carbon atom of the guanidine nucleus are called N. 3 Nitrogen. Note that the guanidine nucleus or N... 2 The α-oxophosphine guanidine group can be part of a larger group (or compound) whose name does not contain guanidine. For example, while the compound 7-dimethyloxophosphine imidazo[1,2-a]imidazole can be classified as a compound having an imidazo[1,2-a]imidazole core (or a compound having an oxophosphine imidazo[1,2-a]imidazole group), 7-dimethyloxophosphine imidazo[1,2-a]imidazole will still be classified as a compound having a guanidine core (or a compound having an N-oxophosphine guanidine group). 2 Compounds containing a β-phosphine guanidine group (because it contains a guanidine nucleus (or N-hydroxyphosphine guanidine group)). 2 The general formula structure defined by the α-oxyphosphine guanidine group.

[0094] Whenever used in this specification and claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of a specific group in a hydrocarbon (e.g., a halohydrocarbon indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in a hydrocarbon).

[0095] For the purposes of this application, an "inert functional group" is a group that substantially does not interfere with the processes described herein, wherein a material having an inert functional group participates in and / or does not complex with a metal compound. The term "does not complex with a metal compound" can include groups that can complex with metal compounds, but in particular, the molecules described herein may not complex with metal compounds due to their positional relationship within the ligand. For example, while an ether group can complex with a metal compound, a group located at the N... 2 In α-phosphinemidine, the para-ether group of the substituted phenylphosphine group can be an inert functional group because a single metal compound cannot react with the para-ether group and N in the same metal complex molecule. 2 The α-phosphine-amidinium group and the β-oxophosphine complex together. Therefore, the inertness of a particular functional group is related not only to its inherent inability to complex with metal compounds, but also to its position within the metal complex. Non-limiting examples of inert functional groups that do not substantially interfere with the process described herein may include halogen groups (fluorine, chlorine, bromine, and iodine), nitro groups, alkyloxy groups (e.g., alkoxy and / or aryloxy groups), sulfide groups, and / or hydrocarbon groups.

[0096] The term "alkyl group" is used herein as defined by IUPAC as follows: a monovalent group (i.e., a group containing only carbon and hydrogen) formed by removing hydrogen atoms from a hydrocarbon. Non-limiting examples of alkyl groups include ethyl, phenyl, tolyl, propenyl, cyclopentyl, etc. The term "alkylene group" is also used herein as defined by IUPAC as follows: "alkylene group" refers to a divalent group formed by removing two hydrogen atoms from a hydrocarbon or a substituted hydrocarbon, whose free valence does not participate in the formation of a double bond. By example and comparison, examples of alkyl groups and alkylene groups include: aryl and arylene groups; alkyl and alkyldiyl ("alkylene groups"); cycloalkyl and cycloalkyldiyl (or "cycloalkylene groups"); aralkyl and aralkyldiyl (or "arylene groups"); etc. For example, "arylene group" is used by IUPAC definition to refer to a divalent group derived from an aromatic hydrocarbon by removing hydrogen atoms from two ring carbon atoms, which may also be called "aryldiyl". Examples of alkylene groups include, but are not limited to: 1,2-phenylene; 1,3-phenylene; 1,2-propanediyl; 1,3-propanediyl; 1,2-ethylenediyl; 1,4-butanediyl; 2,3-butanediyl; and methylene (-CH2-).

[0097] The term "heterohydrogen group" is used herein to refer to a monovalent group, which can be straight-chain, branched, or cyclic, formed by removing a single hydrogen atom from a heteroatom in a parent "heterohydrogen" molecule, wherein at least one carbon atom is replaced by a heteroatom. Therefore, "heteroatom" refers to a non-carbon atom, such as oxygen, sulfur, nitrogen, phosphorus, silicon, etc. Examples of “heteroalkyl” groups formed by removing a single hydrogen atom from a heteroatom of a heteroalkyl molecule include, for example: [1] alkyloxy groups, such as alkoxy (-OR) groups, such as tert-butoxy or aryloxy (-OAr) groups, such as substituted or unsubstituted phenoxy groups formed by removing a hydrogen atom from a hydroxyl (OH) group of a parent alcohol or phenol molecule; [2] alkylthio groups, such as alkylthio (-SR) or arylthio (-SAr) groups formed by removing a hydrogen atom from a hydrogen thio group (-SH) of an alkylthiol or arylthiol; [3] alkylamino groups, such as alkylamino (-NHR) or arylamino (-NHAr) groups formed by removing a hydrogen atom from an amino group (-NH2) of an alkylamine or arylamine molecule; and [4] trialkylsilyl groups, such as trialkylsilyl (-SiR3) or triarylsilyl (-SiAr3).

[0098] "Heteroatom ligands," which can be abbreviated as "HetLig," are ligands that include heteroatoms (non-carbon atoms) such as oxygen, sulfur, nitrogen, phosphorus, silicon, etc. This document discloses various heteroatom ligands that can be utilized in the computational and synthetic aspects of this disclosure.

[0099] "Aliphatic" compounds are a class of acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds, such as non-aromatic organic compounds. An "aliphatic group" is a generalized group formed by removing one or more hydrogen atoms (as required by the specific group) from the carbon atoms of an aliphatic compound. Aliphatic compounds and therefore aliphatic groups may contain organic functional groups and / or atoms other than carbon and hydrogen.

[0100] As used in this specification and claims, the term "alkane" refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of a specific group in an alkane (e.g., haloalkane indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in an alkane). The term "alkyl" is used herein according to the definition given by IUPAC: a monovalent group formed by removing a hydrogen atom from an alkane. Similarly, "alkylene" refers to a group formed by removing two hydrogen atoms from an alkane (two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms). "Aliphatic group" is a general term that refers to a group formed by removing one or more hydrogen atoms from an alkane (as required by the specific group). Unless otherwise indicated, "alkyl," "alkylene," and "alkane group" may be acyclic or cyclic and / or straight-chain or branched. Primary, secondary, and tertiary alkyl groups are derived by removing hydrogen atoms from the primary, secondary, and tertiary carbon atoms of an alkane, respectively. n-alkyl groups can be derived by removing hydrogen atoms from the terminal carbon atom of a straight-chain alkane. The groups that form RCH2(R≠H), R2CH(R≠H) and R3C(R≠H) are primary alkyl, secondary alkyl, and tertiary alkyl, respectively, where R itself is an alkyl group.

[0101] As used herein, the term "carbocyclic" group refers to a group in which a carbocyclic compound is the parent 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 hydrogen atoms from a carbocyclic compound. Non-limiting examples of carbocyclic groups include, for example, cyclopentyl, cyclohexyl, phenyl, tolyl, naphthyl, etc.

[0102] "Cycloalkanes" are saturated cyclic hydrocarbons with or without side chains, such as cyclobutane. Other identifiers can be used to indicate the presence of specific groups in cycloalkanes (e.g., haloalkanes indicate the presence of one or more halogen atoms replacing an equal number of hydrogen atoms). Unsaturated cyclic hydrocarbons with one intracyclic double bond or one triple bond are called cycloalkenes and cycloalkynes, respectively. Those with more than one such multiple bond are cyclodienes, cyclotrienes, etc. Other identifiers can be used to indicate the presence of specific groups in cycloalkenes, cyclodienes, cyclotrienes, etc.

[0103] "Cycloalkyl" is a monovalent group derived by removing a hydrogen atom from the ring carbon atom of a cycloalkane. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. For clarity, other examples of cycloalkyl groups include 1-methylcyclopropyl and 2-methylcyclopropyl, as shown below.

[0104]

[0105] "Cycloalkane group" refers to a generalized group formed by removing one or more hydrogen atoms from a cycloalkane (as required by the specific group and at least one of them being a cyclic carbon).

[0106] Whenever used in this specification and claims, the term "olefin" refers to an olefin having at least one carbon-carbon double bond. Unless otherwise expressly indicated, the term "olefin" includes aliphatic or aromatic, cyclic or acyclic, and / or straight-chain and branched olefins. Unless expressly indicated, the term "olefin" itself does not indicate the presence or absence of heteroatoms and / or other carbon-carbon double bonds. Other identifiers may be used to indicate the presence or absence of specific groups within an olefin. olefins can also be further identified by the position of the carbon-carbon double bonds. Olefins having more than one such multiple bond are dienes, trienes, etc., and can be further identified by the position of the carbon-carbon double bonds.

[0107] "Alkenyl" is a monovalent group derived from an alkene by removing a hydrogen atom from any carbon atom of the alkene. Therefore, "alkenyl" includes groups in which the hydrogen atom is formally derived from sp... 2 Hybridized (alkene) carbon atoms removed from groups and in which hydrogen atoms are formally removed from any other carbon atom (e.g., sp). 3 Alkenyl groups are groups removed from a carbon atom (a carbon atom). For example, unless otherwise specified, 1-propenyl (-CH=CHCH3), 2-propenyl [(CH3)C=CH2], and 3-propenyl (-CH2CH=CH2) are all included within the term "alkenyl". In this respect, 3-propenyl (-CH2CH=CH2) is considered an alkenyl group having a terminal C=C double bond, as is 4-butenyl (-CH2CH2CH=CH2). Other identifiers can be used to indicate the presence or absence of a specific group within an alkene group. Alkenyl groups can also be further identified by the position of the carbon-carbon double bond. Similarly, "cycloalkenyl" is a monovalent group derived from a cycloalkene by removing a hydrogen atom from any carbon atom of the cycloalkene, regardless of whether the carbon atom is sp. 2 Hybrid (alkene) or sp 3 Hybridized carbon atoms.

[0108] The term "olefin" is used herein according to the definition specified by IUPAC: an acyclic and cyclic hydrocarbon having one or more carbon-carbon double bonds in addition to a formal carbon-carbon double bond in an aromatic compound. Therefore, unless otherwise specified, the term "olefin" includes aliphatic and aromatic, acyclic and cyclic, and / or straight-chain and branched compounds having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. The class "olefin" includes alkenes and cycloalkenes, as well as corresponding polyenes. Ethylene, propylene, 1-butene, 2-butene, 1-hexene, etc., are non-limiting examples of olefins. The term "α-olefin" as used in this specification and claims refers to an olefin having a double bond between the first and second carbon atoms of the longest continuous carbon chain. Unless otherwise expressly specified, the term "α-olefin" includes straight-chain and branched α-olefins. Calculations and reaction studies relating to the olefin oligomerization reactions of this disclosure have been performed with ethylene; therefore, unless the context of this disclosure permits or otherwise requires, the use of the term "olefin" generally refers to ethylene.

[0109] In the context of this disclosure, unless otherwise specified, the abbreviation “C6” or “C6” may be used to refer to all hydrocarbon compounds having six carbon atoms, and the abbreviation “C8” or “C8” may be used to refer to all hydrocarbon compounds having eight carbon atoms.

[0110] "Aromatic group" refers to a generalized group formed by removing one or more hydrogen atoms (as required by the specific group and at least one of which is an aromatic ring carbon atom) from an aromatic compound. Therefore, as used herein, "aromatic group" refers to a group derived by removing one or more hydrogen atoms from an aromatic compound, i.e., a compound containing a cyclic conjugated hydrocarbon that follows Hückel's (4n+2) rule and contains (4n+2) π electrons, where n is an integer from 1 to approximately 5. Unless otherwise indicated, aromatic compounds and therefore "aromatic groups" can be monocyclic or polycyclic. Aromatic compounds include "aromatic hydrocarbons" (hydrocarbon aromatic compounds) and "heteroaromatic hydrocarbons," also known as "heteroaromatic hydrocarbons" (heteroaromatic compounds formally derived from aromatic hydrocarbons by replacing one or more methine (-C=) carbon atoms with trivalent or divalent heteroatoms in a manner that preserves the continuous π electron system characteristics of the aromatic system and the number of out-of-plane π electrons corresponding to Hückel's (4n+2) rule). Although aromatic compounds and heteroaromatic compounds are mutually exclusive members of the group of aromatic compounds, a compound having both an aromatic group and a heteroaromatic group is generally considered a heteroaromatic compound. Unless otherwise indicated, aromatic compounds, aromatics, and heteroaromatics can be monocyclic or polycyclic. Examples of aromatics include, but are not limited to, benzene, naphthalene, and toluene. Examples of heteroaromatics include, but are not limited to, furan, pyridine, and methylpyridine. As disclosed herein, the term "substituted" may be used to describe an aromatic group in which any non-hydrogen moiety formally replaces a hydrogen in the group, and is intended to be non-limiting.

[0111] Aromatic hydrocarbons are aromatic hydrocarbons with or without side chains (e.g., benzene, toluene, or xylene). An "aryl" is a group derived from an aromatic hydrocarbon compound by formally removing a hydrogen atom from the carbon atom of the aromatic hydrocarbon ring. An example of an "aryl" is ortho-tolyl (o-tolyl), the structure of which is shown here.

[0112]

[0113] Aromatic hydrocarbons may contain a single aromatic ring (e.g., benzene or toluene), a fused aromatic ring (e.g., naphthalene or anthracene), and one or more separate aromatic rings (e.g., biphenyl) or non-aromatic hydrocarbon groups (e.g., diphenylmethane) linked covalently by bonds.

[0114] A "heterocyclic compound" is a cyclic compound having at least two different elements as ring members. For example, a heterocyclic compound may contain rings containing carbon and nitrogen (e.g., tetrahydropyrrole), carbon and oxygen (e.g., tetrahydrofuran), or carbon and sulfur (e.g., tetrahydrothiophene). Heterocyclic compounds and heterocyclic groups can be aliphatic or aromatic.

[0115] "Aryl" is an alkyl group that has an aryl group substituted with a free valence at a non-aromatic carbon atom. For example, benzyl and 2-phenylethyl are examples of "aryl".

[0116] The term "halogen" has its usual meaning; therefore, examples of halogens include fluorides, chlorides, bromides, and iodides.

[0117] The term "co-catalyst" is generally used herein to refer to compounds such as organoaluminum compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, etc., which may constitute a component of the catalyst composition when used, for example, in conjunction with the chromium-based catalyst compounds of this disclosure. The use of the term "co-catalyst" is unrelated to the actual function of the compound or any chemical mechanism by which the compound may function.

[0118] The terms "catalyst composition," "catalyst mixture," "catalyst system," etc., do not depend on the actual product or composition produced by contact or reaction of the initial components of the claimed catalyst composition / mixture / system, the nature of the active catalytic site, or the fate of the co-catalyst, transition metal catalyst compound, any olefin monomer used in the catalytic reaction, etc. Therefore, the terms "catalyst composition," "catalyst mixture," "catalyst system," etc., encompass the initial starting components of the composition and any products that may be produced by contact with 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.

[0119] "Organoaluminum compounds" are used to describe any compound containing an aluminum-carbon bond. Therefore, organoaluminum compounds include, but are not limited to, alkylaluminum compounds, such as trialkylaluminum compounds, dialkylaluminum compounds, or monoalkylaluminum compounds; halogenated alkylaluminum compounds; alkylaluminoxane compounds; and aluminate compounds containing an aluminum-organic bond, such as tetra(p-tolyl)aluminate. "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 an organic group and the listed metal.

[0120] References to gaseous, liquid, and / or solid materials refer to the physical state of the material at 25°C and atmospheric pressure.

[0121] Features provided as minimum values ​​in this disclosure may alternatively be expressed as "at least" or "greater than or equal to" any of the listed minimum values ​​of the features disclosed herein. Features provided as maximum values ​​in this disclosure may alternatively be expressed as "less than or equal to" the values ​​of the features disclosed herein.

[0122] Within this disclosure, the general rules of organic nomenclature will apply. For example, when referring to a substituted compound or group, a reference to the substitution pattern is used to indicate that the indicated group is located at the indicated position and all other unindicated positions are hydrogen. For example, a reference to a 4-substituted phenyl indicates that a non-hydrogen substituent is located at position 4 and hydrogen is located at positions 2, 3, 5, and 6. As another example, a reference to a 3-substituted naphth-2-yl indicates that a non-hydrogen substituent is located at position 3 and hydrogen is located at positions 1, 4, 5, 6, 7, and 8. References to compounds or groups having substitutions at positions other than those indicated will be referred to using some other alternative language. For example, a reference to a phenyl containing a substituent at position 4 refers to a group having a non-hydrogen atom at position 4 and hydrogen or any non-hydrogen group at positions 2, 3, 5, and 6.

[0123] This article describes a process for forming oligomeric products. Such processes typically involve contacting ethylene with a catalyst system (or alternatively, contacting ethylene with components of the catalyst system) to form oligomeric products under oligomerization conditions.

[0124] The term "oligomery" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight of a product comprising 2 to 30 ethylene units. Similarly, as used herein, "oligomer" is a product containing 2 to 30 ethylene units, while "oligomeric product" or "oligomery product" includes all products produced by said process, including both "oligomers" and products that are not "oligomers" (e.g., products containing more than 30 ethylene units). Furthermore, the terms "oligomery product" and "oligomery product" are used interchangeably.

[0125] The term "trimer" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight of a product containing three and only three ethylene units. A "trimer" is a product containing three and only three ethylene units, while a "trimer product" includes all products produced by the trimerization process, including trimers and non-trimer products (e.g., dimers or tetramers). Typically, the "trimerization" process using ethylene produces an oligomeric product containing at least 70% by weight of hexene.

[0126] The term "tetramer" and its derivatives refer to a process that produces a mixture of products containing at least 70% by weight of a product containing four and only four ethylene units. A "tetramer" is a product containing four and only four ethylene units, while "tetramer product" includes all products produced by the tetramer process, including tetramers and non-tetramers (e.g., dimers or trimers). Typically, the "tetramer" process using ethylene produces an oligomeric product containing at least 70% by weight of octene.

[0127] The terms “trimer and tetramer” and their derivatives refer to processes that produce mixtures of products containing at least 70% by weight of a product containing three and / or four, and only three and / or four ethylene units. “Trimer and tetramer products” include all products produced by “trimer and tetramer” processes, including trimers, tetramers, and non-tetramer products (e.g., dimers). Typically, “trimer and tetramer” processes using ethylene produce oligomer products containing at least 70% by weight of hexene and / or octene.

[0128] Unless otherwise specified, the terms contact, combination, and "in the presence of" refer to any order, sequence, or concentration of addition of two or more components used in the contacting or combination of oligomerization processes. According to the various methods described herein, the combination or contact of oligomer components can be carried out in one or more contact zones under suitable contact conditions, such as temperature, pressure, contact time, flow rate, etc. The contact zone can be located in a vessel (e.g., a tank, bag, container, mixing vessel, reactor, etc.), a section of tubing (e.g., a tee, inlet, injection port, or manifold for combining component feed lines into a common line), or any other suitable device for contacting the components. The process can be carried out as a batch or continuous process, as appropriate for a given embodiment.

[0129] The use of the term "optionally" with respect to any element of the claims 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 claims.

[0130] Although this disclosure uses the Gibbs free energy for many of its calculations, enthalpy and / or Helmholtz energy can also be used as approximations of the Gibbs free energy.

[0131] The processes described herein may utilize steps, features, compounds, and / or apparatus independently described herein. The processes described herein may or may not utilize step identifiers (e.g., 1), 2), a), b), i), ii), or first, second, etc., feature identifiers (e.g., 1), 2), a), b), i), ii), or first, second, etc., and / or compound and / or composition identifiers (e.g., 1), 2), a), b), i), ii), or first, second, etc., and / or second, etc., and / or composition identifiers (e.g., 1), 2), a), b), i), ii), or first, second, etc., and / or other identifiers). However, it should be noted that the processes described herein may have multiple steps, features (e.g., reagent ratios, formation conditions, and other considerations), and / or multiple compounds and / or compositions, without using descriptors or sometimes having the same generic identifiers. Therefore, it should be noted that the process described herein may be modified to use appropriate step or feature identifiers (e.g., 1), 2), a), b), i), ii), or first, second, etc. and / or compound identifiers (e.g., first, second, etc.) regardless of the step, feature, and / or compound identifiers used in the particular aspect and / or embodiment described herein, and step or feature identifiers may be added and / or modified to indicate the various different steps / features / compounds used in the process, thereby detrimental to the overall disclosure.

[0132] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, constructs and methods described in the publications that can be used in conjunction with the invention described herein. The publications discussed throughout are provided solely for their disclosure prior to the filing date of this application. Nothing herein should be construed as an admission that the inventor has no right to any prior disclosure by virtue of a prior invention.

[0133] General method description

[0134] When designing novel heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes) of catalyst systems that can produce products with enhanced activity / productivity, product purity, and selectivity (e.g., increased selectivity for 1-hexene or 1-octene), the design process may involve an iterative approach to identifying and tuning key synthetic or electronic characteristics of the heteroatom ligand-metal compound complex that affect the relative energies of the ground and transition states for activity / productivity, selectivity (production of 1-octene compared to 1-hexene), and product purity (1-hexene compared to other C6 products and / or 1-octene compared to other C8 products). This design process can also be used to improve the selectivity of trimerization catalytic cycles for 1-hexene (also known as trimerization cycle selectivity for 1-hexene), the selectivity of tetramerization catalytic cycles for 1-octene, and / or the efficiency of 1-octene in the fourth ethylene addition. These key structural or electronic features can be used as input variables for developing computational designs that examine their relative importance in influencing the relative energies of the ground and transition states, and thus their impact on the overall activity / productivity, product purity, and selectivity of the oligomerization process. Based on such computational designs, target heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes) can be identified by desired adjustments to their structural or electronic features, and these target complexes can be synthesized and experimentally verified. Based on these results, computational redesign or iteration can be used to identify next-generation target complexes, which can also be experimentally verified and further tested and redesigned.

[0135] Therefore, in one aspect, this disclosure provides a method for designing heteroatom ligand-metal compound complexes for olefin oligomerization, the method comprising:

[0136] (a) Select n input variables I 1 I 2 ...I n (n is an integer), each input variable corresponds to one or more ground state model structures GS. A1 ...GS Ap (p is an integer) and multiple transition state model structures TS associated with the one or more ground state model structures.A1 TS A2 ...TS Am (m is an integer) structural or electronic properties

[0137] The one or more ground state model structures GS A1 ...GS Ap Each of the multiple transition state model structures TS A1 TS A2 ...TS Am Each of them is derived from one or more first-trained heteroatom ligand-metal compound complexes, and each complex contains a first-trained heteroatom ligand;

[0138] (b) For the ground state model structure GS A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am Each of the n input variables I represents a given set of n input variables. 1 I 2 ...I n Allocate quantitative values;

[0139] (c) The ground state model structure GS is determined by at least one processor of the device. A1 ...GS AP Each of them and the transition state model structure TS A1 TS A2 ...TS Am The relative energy of each of them;

[0140] (d) Based on the input variables I for every n... 1 I 2 ...I n The quantitative value and the ground state model structure GS A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am The relative energies of each of them are interconnected, generating a machine learning model;

[0141] (e) Based on the machine learning model, identify the n input variables I. 1 I 2 ...I n One or more input variables related to the following: [1] the ground state model structure GS A1 ...GS ApOne of the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between at least one of them [ΔG(TS-GS) or ΔΔG(TS-GS)] or [2] the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between any two or more of them [ΔG(TS-TS) or ΔΔG(TS-TS)];

[0142] (f) Based on the one or more n input variables I identified from step (e) 1 I 2 ...I n Generate a first target heteroatom ligand-metal compound complex for olefin oligomerization and comprising a first target heteroatom ligand, wherein the first target heteroatom ligand-metal compound complex is characterized by n output variables O 1 O 2 ...O n Each output variable has a corresponding ground state model structure GS. B1 ...GS Bx (x is an integer) or multiple transition state model structures TS associated with one or more ground state model structures. B1 TS B2 ...TS By A quantitative value of any one of the structural or electronic properties (y is an integer).

[0143] The one or more ground state model structures GS B1 ...GS Bx Each of the multiple transition state model structures TS B1 TS B2 ...TS By Each of them is derived from the first target heteroatom ligand-metal compound complex, and each complex contains the first target heteroatom ligand;

[0144] (g) For the one or more first training heteroatom ligand-metal compound complexes and the first target heteroatom ligand-metal compound complexes, identify one or more performance parameters related to the olefin oligomerization reaction and the values ​​of the performance parameters; and

[0145] (h) Using the n output variables O of the first target heteroatom ligand-metal compound complex 1 O 2 ...O nThe quantitative value is derived from n new input variables I for olefin oligomerization and one or more second-trained heteroatom ligand-metal compound complexes containing second-trained heteroatom ligands. 1.1 I 2.1 ...I n.1 Given an input dataset, repeat steps (a)-(f) once or more, and evaluate the input dataset against a machine learning model to generate a second target heteroatom ligand-metal compound complex containing a second target heteroatom ligand, wherein the second target heteroatom ligand-metal compound complex is characterized by new n output variables O 1.1 O 2.1 ...O n.1 The output dataset contains quantitative values ​​and performance parameter values ​​for one or more second-target heteroatom ligand-metal compound complexes.

[0146] In this respect, for every n input variables I 1 I 2 ...I n In step (b) of assigning quantitative values, these assigned quantitative values ​​can be independently assigned either original values ​​or normalized values. Also in this respect, in determining the ground-state model structure GS... A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am In step (c) of determining the relative energy of each of the n input variables, these determined relative energies can independently be the relative energies of the possible conformational ensembles of the ground state model structure and the transition state model structure, or the relative energies of a specific conformation. Further in this respect, in step (e), the n input variables I are identified... 1 I 2 ...I n One or more input variables related to [1]ΔG(TS-GS) or ΔΔG(TS-GS) or [2]ΔG(TS-TS) or ΔΔG(TS-TS), whose energy differences can be based on the Boltzmann ensemble ΔG or ΔΔG values.

[0147] For convenience, the above method may generally be referred to as the "calculation" method of this disclosure. In another aspect, the above calculation method may further include the following steps:

[0148] (i)[1] Synthesize the first target heteroatom ligand and / or the second target heteroatom ligand; or [2] Synthesize the first target heteroatom ligand and / or the second target heteroatom ligand, and then synthesize the first target heteroatom ligand-metal compound complex or the second target heteroatom ligand-metal compound complex.

[0149] In another aspect, after synthesis step (i), the above method may also include the following steps:

[0150] (j) The olefin oligomerization reaction is carried out 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.

[0151] Regarding input variables, in the calculation methods disclosed above, at least one input variable I... 1 I 2 ...I n This can correspond to one or more ground state model structures GS listed in the calculation method. A1 ...GS Ap At least one of the structural or electronic properties. The at least one input variable I 1 I 2 ...I n It can also correspond to the multiple transition state model structures TS listed in the calculation method. A1 TS A2 ...TS Am At least one of the structural or electronic properties. For the one or more ground-state model structures GS derived from the one or more first-trained heteroatom ligand-metal compound complexes. A1 ...GS Ap Each of the multiple transition state model structures TS A1 TS A2 ...TS Am Each of the n input variables I is assigned to each of the n input variables. 1 I 2 ...I n The quantitative values ​​can be assigned based on calculated values, measured values, or estimated values, or any combination thereof, and these assigned quantitative values ​​can be independently assigned to the original values ​​or normalized values.

[0152] According to one aspect, step (e) of the above calculation method can identify the n input variables I based on a machine learning model. 1 I 2...I n In the context of the one or more ground state model structures GS A1 ...GS Ap Any one of the and the plurality of transition state model structures TS A1 TS A2 ...TS Am One or more input variables are related to the energy difference [ΔG(TS-GS) or ΔΔG(TS-GS)] between at least one of them. Step (e) of the above-disclosed calculation method can also identify the n input variables I based on a machine learning model. 1 I 2 ...I n The multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference [ΔΔG(TS-TS)] between any two or more input variables is related to one or more input variables.

[0153] Therefore, on the one hand, this method can identify and select n input variables I. 1 I 2 ...I n One or more input variables, which impart 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, can provide efficiency to the method and guide the design of next-generation compounds in terms of synthesis and computation to provide improved performance for desired parameters (e.g., activity / yield, product purity, and / or selectivity). For example, the n input variables I identified in step (e) 1 I 2 ...I n The one or more mentioned above can be identified based on the following large percentage changes: [1] the one or more ground state model structures GS A1 ...GS Ap Any one of the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between at least one of them [ΔG(TS-GS) or ΔΔG(TS-GS)] or [2] the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference [ΔG(TS-TS) or ΔΔG(TS-TS)] between any two or more of the n input variables I is given by the energy difference between the n input variables I and ... 1 I 2 ...I nEach percentage change of one or more of the above will affect ΔG(TS-GS), ΔΔG(TS-GS), or ΔΔG(TS-TS).

[0154] Model ground-state and model transition-state structures in heteroatom ligand-metal compound complexes

[0155] Specific heteroatom ligand-metal compound complexes (e.g., heteroatom ligand-chromium compound complexes) that can be used for computational and synthetic purposes in this study, such as one or more first-trained heteroatom ligand-metal compound complexes, may have a general formula independently selected from:

[0156] [(HetLig)CrX q L r ] 3-q (A); where:

[0157] HetLig represents one or more of the first training heteroatom ligands;

[0158] X is an anionic ligand, and q is an integer;

[0159] L is a neutral ligand, and r is an integer.

[0160] Any two or more of the X and L ligands can be linked to form a polydentate ligand.

[0161] On the one hand,

[0162] Each selected n input variables I 1 I 2 ...I n , corresponding to the one or more ground state model structures GS A1 ...GS Ap Any of the ground state model structures TS associated with one or more ground state model structures of equation (A) A1 TS A2 ...TS Am The structural or electronic properties of any one of them.

[0163] As explained herein, specific input variables that can be used in the computational method may include, or be selected from, the structural and electronic characteristics of the heteroatom ligand-metal compound complex (e.g., heteroatom ligand-chromium compound complex) of formula (A), including: various atomic distances (e.g., the distance between chromium and heteroatoms in the heteroatom ligand); certain chromium heteroatom ligand bond angles; various chromium heteroatom ligand atomic dihedral angles; atomic charges on Cr and / or heteroatoms in the heteroatom ligand-chromium compound complex; and / or specific parameters, such as the outside-of-bag distance. And the percentage of buried volume. This paper further provides these structural features, electronic characteristics, and parameters.

[0164] In one aspect of the computational method described herein, the method employs a series of model structures, applies the method to these model structures, and derives new structures from these model structures. These structures are described as follows:

[0165] [1] The ground-state model structure GS derived from one or more first training heteroatom ligand-metal compound complexes A1 ...GS Ap ;

[0166] [2] The ground-state model structure GS derived from one or more first-target heteroatom ligand-metal compound complexes B1 ...GS Bx ;

[0167] [3] Transition state model structure TS derived from one or more first training heteroatom ligand-metal compound complexes A1 TS A2 ...TS Am ;and

[0168] [4] Transition state model structure TS derived from one or more first training heteroatom ligand-metal compound complexes A1 TS A2 ...TS Am .

[0169] Each of these model structures contains a heteroatom ligand, which can be specified according to the specific complex. For example, the heteroatom ligand in each complex can be specified as the first training heteroatom ligand in the model structures listed herein [1] and [3], or as the first target heteroatom ligand in the model structures listed herein [2] and [4].

[0170] In one aspect, the one or more ground-state model structures GS derived from the one or more first training heteroatom ligand-metal compound complexes are... A1 ...GS Ap It can be selected from any of the following model structures:

[0171]

[0172] Where HetLig represents one or more first training heteroatom ligands, and wherein the model ground state structure GS I -I to GS IThe superscript "I" in each of -XIII indicates "instructional", that is, "training" the ground state structure of the model.

[0173] On the other hand, the multiple transition state model structures TS derived from the one or more first training heteroatom ligand-metal compound complexes A1 TS A2 ...TS Am Can be selected independently from:

[0174]

[0175]

[0176] Where HetLig represents one or more first training heteroatom ligands, and wherein the model transition state structure TS I -I to TS I The superscript "I" in each of the -XV values ​​indicates "instructional", that is, the transitional structure for "training" the model.

[0177] A similar set of model ground-state structures and model transition-state structures can be used as the target heteroatom ligand-metal compound complex. Therefore, the one or more ground-state model structures GS derived from the one or more first target heteroatom ligand-metal compound complexes are... B1 ...GS Bx Can be selected independently from:

[0178]

[0179]

[0180] Wherein HetLig represents one or more first target heteroatom ligands, and wherein the model ground state structure GS T -I to GS T The superscript "T" in each of -XIII indicates the ground state structure of the target model.

[0181] In another aspect, the plurality of transition state model structures TS derived from the one or more first target heteroatom ligand-metal compound complexes... A1 TS A2 ...TS Am Can be selected independently from:

[0182]

[0183]

[0184] Where HetLig represents one or more first training heteroatom ligands, and wherein the model transition state structure TS T -I to TS T The superscript "T" in each of the -XV values ​​indicates "instructional", that is, the transitional structure for "training" the model.

[0185] Heteroatom ligands and heteroatom ligand-metal compound complexes

[0186] Typically, the heteroatom ligand of a heteroatom ligand or heteroatom ligand-metal compound complex (e.g., heteroatom ligand-chromium compound complex) can be any heteroatom ligand that can form an oligomeric product in the reaction zone when used in the catalyst system (or mixture of catalyst systems) described herein and / or the reaction system described herein. In one aspect, the heteroatom ligand of a heteroatom ligand or heteroatom ligand-metal compound complex (e.g., heteroatom ligand-chromium compound complex) can be a neutral heteroatom ligand or an anionic heteroatom ligand; alternatively, a neutral heteroatom ligand; or alternatively, an anionic heteroatom ligand. In one aspect, a neutral heteroatom ligand may comprise one or more heteroatom complexing moieties; alternatively, two heteroatom complexing moieties; or alternatively, three heteroatom complexing moieties. In one aspect, an anionic heteroatom ligand may also comprise one or more neutral heteroatom complexing moieties; alternatively, two heteroatom complexing moieties; or alternatively, three heteroatom complexing moieties. In one aspect, each neutral heteroatom complex of the neutral ligand or anionic ligand comprising a neutral heteroatom complex can independently be an ether, thio, amino, imino, phosphine, hypophosphonic acid, phosphite, or phosphite; alternatively, an ether, thio, amino, imino, or phosphine; alternatively, an ether; alternatively, a thio; alternatively, an amino; alternatively, an imino; or alternatively, a phosphine. In another aspect, the anionic atom of the anionic heteroatom ligand (which forms a covalent or ionic bond with chromium in the chromium compound) can 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.

[0187] On one hand, for example, heteroatom ligand-metal compound complexes can be heteroatom ligand chromium compound complexes and can have 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 and q is an integer, L is a neutral ligand and r is an integer, and where any two or more of the X and L ligands can be connected to form a polydentate ligand. Therefore, for the general and specific structures disclosed below, it is foreseeable that any two or more of the X and L ligands can form a chelate ligand, wherein the bridging portion connects the X ligand, the L ligand, or a combination of the X and L ligands.

[0188] In any respect, the heteroatom ligand or heteroatom ligand chromium compound complex may contain, be composed of, or be: N 2 -Oxyphosphine formamidin, N 2 -Oxyphosphinemidine, N 2 -Oxyphosphinoguanidine, heterocyclic 2-[(oxophosphino)amino]imine or any combination thereof; alternatively, N 2 -Oxyphosphine formamidinium; alternatively, N 2 -Oxyphosphinemidine; alternatively, N 2 -Oxyphosphine guanidine; or alternatively, heterocyclic 2-[(oxophosphine)amino]imine. Typically, N... 2 -Oxyphosphine formamidinium can have the structure NPF-1,N 2 -Oxyphosphinemidane can have the structure NPA-1,N 2 -Oxyphosphinoguanidine may have structures Gu-1, Gu-2, Gu-3, Gu-4, or Gu-5, and the heterocyclic 2-[(oxophosphino)amino]imine may have the structure HCPA-1. In some aspects, N 2 -Oxyphosphoguanidine has a structure Gu-2, Gu-3, or Gu-4; alternatively, a structure Gu-1; alternatively, a structure Gu-2; alternatively, a structure Gu-3; alternatively, a structure Gu-4; or alternatively, a structure Gu-5.

[0189]

[0190] In any respect, heteroatom ligand chromium compound complexes may contain, may consist substantially of, or may be composed of: N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphinoguanidine chromium compound complexes, heterocyclic 2-[(oxophosphino)amino]imine chromium compound complexes, or any combination thereof; alternatively, N 2 -Oxyphosphine-formamidinium chromium compound complex; alternatively, N 2 -Oxyphosphine-based amidine chromium compound complex; alternatively, N 2 -Oxyphosphine-guanidine chromium compound complex; alternatively, N2 -Oxyphosphine-guanidine chromium compound complexes; or alternatively, heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes. Typically, N... 2 -Oxyphosphine-formamidinium chromium compound complexes can have the structure NPFCr-1,N 2 -Oxyphosphine-based amidine chromium compound complexes can have the structure NPACr-1,N 2 -Oxyphosphine-guanidine chromium compound complexes may have structures GuCr-1, GuCr-2, GuCr-3, GuCr-4, or GuCr-5, and heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes may have the structure HCPACr-1. In some aspects, N 2 -Oxyphosphine-based guanidine chromium compound complexes have the structure GuCr-2, GuCr-3, or GuCr-4; alternatively, the structure GuCr-1; alternatively, the structure GuCr-2; alternatively, the structure GuCr-3; alternatively, the structure GuCr-4; or alternatively, the structure GuCr-5.

[0191]

[0192] In N 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphinemidine, N 2 In α-oxophosphine-amidinium chromium compound complexes and heterocyclic 2-[(oxophosphine)amino]imine-chromium compound complexes, the nitrogen that forms a double bond with the central carbon atom is called N. 1 Nitrogen that forms a single bond with the central carbon atom is called N. 2 Nitrogen. Similarly, in N... 2 -Oxyphosphine guanidine and N 2 In α-oxophosphine-guanidine-chromium compounds, the nitrogen that forms a double bond with the central carbon atom of the guanidine nucleus is called N. 1 Nitrogen, the nitrogen atom that forms a single bond with the central carbon atom of the guanidine nucleus and a single bond with the phosphorus atom of the phosphine group, is called N. 2 Nitrogen, and the remaining nitrogen atoms that form single bonds with the central carbon atom of the guanidine nucleus are called N. 3 Nitrogen. It should be noted that N... 2 -Oxyphosphine guanidine and N 2In α-oxophosphine-guanidine-chromium complexes, the guanidine group can be part of a larger group that does not contain guanidine in the name. For example, although the compound 7-dimethyloxophosphine-imidazo[1,2-a]imidazole can be classified as a compound having an imidazo[1,2-a]imidazole core (or a compound having an oxophosphine-imidazo[1,2-a]imidazole group), 7-dimethyloxophosphine-imidazo[1,2-a]imidazole will still be classified as a compound having a guanidine core (or a compound having a guanidine group) because it contains the general formula structure defined for guanidine compounds.

[0193] N 2 -Oxyphosphine-formamidinium structure and N 2 R in the structure of -oxophosphine-formamidinium chromium compound complex 1 R 3 R 4 and R 5 Group, N 2 -Oxyphosphine-based amidine structure and N 2 R in the structure of -oxophosphine-based amidine chromium compound complex 1 R 2 R 3 R 4 and R 5 N 2 -Oxyphosphine guanidine structure and N 2 R within the structure of the -oxophosphine guanidine chromium compound complex 1 R 2a R 2b R 3 R 4 R 5 L 12 L 22 and L 23 And L within the heterocyclic 2-[(oxophosphino)amino]imine structure and the heterocyclic 2-[(oxophosphino)amino]imine chromium compound complex structure 12 T, R 3 R 4 and R 5 It can be used in any combination and without restriction to further describe the N disclosed herein. 2 -Oxyphosphine-formamidinium structure, N 2 -Oxyphosphine-formamidinium compound complex structure, N 2 -Oxyphosphine-based amidine structure, N 2 -Oxyphosphine-based amidine chromium compound complex structure, N 2 -Oxyphosphine guanidine structure, N 2 Structures of -oxophosphine-guanidine chromium compounds, heterocyclic 2-[(oxophosphine)amino]imine compounds, and heterocyclic 2-[(oxophosphine)amino]imine chromium compounds. N 2 -Oxyphosphine-formamidinium compound complex structure, N2 -Oxyphosphine-based amidine chromium compound complex structure, N 2 X. Structure of α-oxophosphine-guanidine chromium compound complex and structure of heterocyclic 2-[(oxophosphine)amino]imine chromium compound complex p Q and q are described independently herein and can be used in any combination without limitation to further describe the N disclosed herein. 2 -Oxyphosphine-formamidinium compound complex structure, N 2 -Oxyphosphine-based amidine chromium compound complex structure, N 2 The structures of α-oxophosphine-guanidine chromium compound complexes and heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes. Additionally, regarding X... p Independent descriptions of Q and q can be used without restriction with independent descriptions of R. 1 R 2 R 2a R 2b R 3 R 4 R 5 L 12 L 22 and L 23 Combining to further describe the appropriate N considered in this paper 2 -Oxyphosphine-formamidinium compound complex structure, N 2 -Oxyphosphine-based amidine chromium compound complex structure, N 2 Structures of α-oxophosphine-guanidine chromium compounds and heterocyclic 2-[(oxophosphine)amino]imine chromium compounds.

[0194] Typically, having R 1 N of the group 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphinemidine, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphine guanidine and / or N 2 R of -oxophosphine-guanidine chromium compound complex 1 It can be an organic group; alternatively, an organic group composed of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R... 1 The organic group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On the one hand, R is composed of inert functional groups. 1 Organic groups can be C1 to C1 composed of inert functional groups. 20 C1 to C 15 C1 to C 10Or C1 to C5 organic groups. On one hand, R 1 The hydrocarbon group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 hydrocarbon groups.

[0195] On the one hand, it has R 1 N of the group 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphinemidine, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphine guanidine and / or N 2 R of -oxophosphine-guanidine chromium compound complex 1 It can be alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; alternatively, alkyl, cycloalkyl, aryl, or aralkyl; alternatively, alkyl; alternatively, substituted alkyl; alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl. In any aspect disclosed herein, R 1 Alkyl groups can be C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, substituted R 1 Alkyl groups can be substituted C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, R 1 Cycloalkyl groups can be C4 to C5. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, substituted R 1 Cycloalkyl groups can be substituted C4 to C5. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, R 1 The aryl group can be C6 to C6. 20 C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, the substituted R 1 The aryl group can be a substituted C6 to C6 group. 20C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, R 1 Aryl alkyl groups can be C7 to C6. 20 C7 to C 15 Or C7 to C 10 Aryl alkyl groups. In any respect disclosed herein, substituted R 1 Aryl alkyl groups can be substituted C7 to C8. 20 C7 to C 15 Or C7 to C 10 Aryl alkyl. Each substituent of the substituted alkyl (general or specific), substituted cycloalkyl (general or specific), substituted aryl (general or specific), and / or substituted aryl (general or specific) may be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, alkyl group or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (general and specific), and alkyloxy group substituents (general and specific) are disclosed independently herein. These halogen substituents, alkyl group substituents, and alkyloxy group substituents may be used without limitation to further describe the substituted R 1 Group.

[0196] On the one hand, R 1 It can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; or alternatively, methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), tert-butyl (2-methyl-2-propyl), or neopentyl (2,2-dimethyl-1-propyl). In some respects, it can be used as R. 1 The alkyl group can be substituted. Each substituent of the substituted alkyl group (generally or specifically) can independently be a halogen or alkyloxy group; alternatively, a halogen; or alternatively, an alkyloxy group. Halogen substituents and alkyl substituents (generally and specifically) are disclosed independently herein. These halogen and alkyloxy substituents can be used without limitation for further description and can be used as R 1 Substituted alkyl groups.

[0197] On the one hand, R 1 It can be cyclopentyl, substituted cyclopentyl, cyclohexyl, or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; or alternatively, cyclohexyl or substituted cyclohexyl. In one aspect, it can be used as R. 1The substituted cycloalkyl group can 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 one aspect, used as R... 1 One or more substituents of the polysubstituted cycloalkyl group may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl group may be different. Each substituent of the substituted cycloalkyl group having a specified number of ring carbon atoms may independently be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (generally and specifically), and alkyloxy group substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl group substituents, and alkyloxy group substituents may be used without limitation for further description and may be used as R 1 Substituted cycloalkyl groups (general and specific).

[0198] In a non-restrictive aspect, R 1 It can be cyclohexyl, 2-alkylcyclohexyl, or 2,6-dialkylcyclohexyl; or alternatively, cyclopentyl, 2-alkylcyclopentyl, or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents may be used without limitation for further description as R. 1 The alkylcyclohexyl (general and specific), dialkylcyclohexyl (general and specific), alkylcyclopentyl (general or specific), and / or dialkylcyclopentyl (general and specific). Typically, the alkyl substituents of dialkylcyclohexyl or dialkylcyclopentyl may be the same; or alternatively, the alkyl substituents of dialkylcyclohexyl or dialkylcyclopentyl may be different. In some non-limiting aspects, R 1 It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-ditert-butylcyclohexyl. In other non-limiting respects, R 1 It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl or 2-tert-butylcyclohexyl; or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-ditert-butylcyclohexyl.

[0199] On the one hand, R 1 It can be phenyl, substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In one aspect, it can be used as R. 1 The substituted phenyl group can be a 2-substituted phenyl, a 3-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, a 2,6-disubstituted phenyl, a 3,5-disubstituted phenyl, or a 2,4,6-trisubstituted phenyl; alternatively, a 2-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, or a 2,6-disubstituted phenyl; alternatively, a 3-substituted phenyl or a 3,5-disubstituted phenyl; alternatively, a 2-substituted phenyl or a 4-substituted phenyl; alternatively, a 2,4-disubstituted phenyl or a 2,6-disubstituted phenyl; or alternatively, a 2,4,6-trisubstituted phenyl. In one aspect, used as R 1 One or more substituents of the polysubstituted phenyl group may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl group may be different. Each substituent of the substituted phenyl group (general or specific) may independently be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (general and specific), and alkyloxy group substituents (general and specific) are disclosed independently herein. These halogen substituents, alkyl group substituents, and alkyloxy group substituents may be used without limitation for further description and may be used as R 1 Substituted phenyl groups (general and specific).

[0200] In a non-restrictive aspect, R 1 It can be phenyl, 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, 3,5-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl or 4-alkylphenyl; alternatively, 2,4-dialkylphenyl or 2,6-dialkylphenyl; alternatively, 3-alkylphenyl or 3,5-dialkylphenyl; alternatively, 2-alkylphenyl or 2,6-dialkylphenyl; or alternatively, 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents may be used without limitation for further description as R 1Any alkyl-substituted phenyl group. Typically, the alkyl substituents of dialkylphenyl (generally or specifically) or trialkylphenyl (generally or specifically) may be the same; or alternatively, the alkyl substituents of dialkylphenyl or trialkylphenyl may be different. In some non-limiting respects, R 1 It may independently be 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.

[0201] On the one hand, R 1 It can be benzyl or substituted benzyl; alternatively, benzyl; or alternatively, substituted benzyl. Each substituent of the substituted benzyl can independently be halogen, alkyl, or alkyloxy; alternatively, halogen or alkyl; alternatively, halogen or alkyloxy; alternatively, alkyl or alkyloxy; alternatively, halogen; alternatively, alkyl; or alternatively, alkyloxy. Halogen substituents, alkyl substituents (generally and specifically), and alkyloxy substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl substituents, and alkyloxy substituents can be used without limitation for further description and can be used as R 1 Substituted benzyl groups (general and specific).

[0202] Typically, N 2 -Oxyphosphinemidine and / or N 2 R of -oxophosphine-based amidine chromium compound complexes 2 It can be an organic group; alternatively, an organic group composed of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R... 2 The organic group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On the one hand, R is composed of inert functional groups. 2 Organic groups can be C1 to C1 composed of inert functional groups. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On one hand, R 2 The hydrocarbon group can be C1 to C2.20 C1 to C 15 C1 to C 10 Or C1 to C5 hydrocarbon groups.

[0203] On the one hand, N 2 -Oxyphosphinemidine and / or N 2 R of -oxophosphine-based amidine chromium compound complexes 2 It can be an acyl group or a substituted acyl group; an acyl group; or alternatively, a substituted acyl group. In one aspect, the acyl group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 acyl groups. On one hand, the substituted acyl group can be a substituted C1 to C5 acyl group. 20 C1 to C 15 C1 to C 10 Or C1 to C5 acyl groups. In some respects, N 2 -Oxyphosphinemidine and / or N 2 R of -oxophosphine-based amidine chromium compound complexes 2 It can be alkanoyl, substituted alkanoyl, benzoyl, or substituted benzoyl; alternatively, alkanoyl or substituted alkanoyl; alternatively, benzoyl or substituted benzoyl; alternatively, alkanoyl; alternatively, substituted alkanoyl; alternatively, benzoyl; or alternatively, substituted benzoyl. In any aspect disclosed herein, R 2 The alkyl acyl group can be C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl acyl groups. In any respect disclosed herein, the substituted R 2 The alkyl acyl group can be a substituted C1 to C2 group. 20 C1 to C 10 Or C1 to C5R 2 Alkyl group. In any respect disclosed herein, R 2 The benzoyl group can be C7 to C8. 20 C7 to C 15 Or C7 to C 10 Benzoyl group. In any respect disclosed herein, the substituted R 2 The benzoyl group can be a substituted C7 to C8 group. 20 C1 to C 15 Or C1 to C 10 R 2Benzoyl group. Each substituent of the substituted alkyl acyl group (generally or specifically) and / or the substituted benzoyl group (generally or specifically) can be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, alkyl group or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl substituents (generally and specifically), and alkyloxy group substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl substituents, and alkyloxy group substituents can be used without limitation for further description and can be used as R 2 The substituted alkyl acyl group and / or the substituted benzoyl group.

[0204] On the one hand, N 2 -Oxyphosphinemidine and / or N 2 R of -oxophosphine-based amidine chromium compound complexes 2 It can be alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; or alternatively, alkyl, cycloalkyl, aryl, or aralkyl. In other respects, N 2 -Oxyphosphinemidine and / or N 2 R of -oxophosphine-based amidine chromium compound complexes 2 It can 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. In any respect disclosed herein, R 2 Alkyl groups can be C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, substituted R 2 Alkyl groups can be substituted C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, R 2 Cycloalkyl groups can be C4 to C5. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, substituted R 2 Cycloalkyl groups can be substituted C4 to C5. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, R 2 The aryl group can be C6 to C6. 20C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, the substituted R 2 The aryl group can be a substituted C6 to C6 group. 20 C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, R 2 Aryl alkyl groups can be C7 to C6. 20 C7 to C 15 Or C7 to C 10 Aryl alkyl groups. In any respect disclosed herein, substituted R 2 The aryl group can be a substituted C7 to C8 group. 20 C7 to C 15 Or C7 to C 10 Arane. Each substituent of the substituted alkyl (general or specific), substituted cycloalkyl (general or specific), substituted aryl (general or specific), and / or substituted arane (general or specific) may be halogen, alkyl, or alkyloxy; alternatively, halogen or alkyl; alternatively, halogen or alkyloxy; alternatively, alkyl or alkyloxy; alternatively, halogen; alternatively, alkyl; or alternatively, alkyloxy. Halogen substituents, alkyl substituents (general and specific), and alkyloxy substituents (general and specific) are disclosed independently herein. These halogen substituents, alkyl substituents, and alkyloxy substituents may be used without limitation for further description of R. 2 .

[0205] On the one hand, R 2 It can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; or alternatively, methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), tert-butyl (2-methyl-2-propyl), or neopentyl (2,2-dimethyl-1-propyl). In some respects, it can be used as R. 2 The alkyl group can be substituted. Each substituent of the substituted alkyl group can independently be a halogen or an alkyloxy group; alternatively, a halogen; or alternatively, an alkyloxy group. Halogen substituents and alkyl substituents (general and specific) are disclosed independently herein. These halogen and alkyloxy substituents can be used without limitation for further description and can be used as R 2 Substituted alkyl groups (general and specific).

[0206] On the one hand, R 2 It can be cyclopentyl, substituted cyclopentyl, cyclohexyl, or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; or alternatively, cyclohexyl or substituted cyclohexyl. In one aspect, it can be used as R. 2The substituted cycloalkyl group can 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 one aspect, used as R... 2 One or more substituents of the polysubstituted cycloalkyl group may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl group may be different. Each substituent of the cycloalkyl group having a specified number of cyclic carbon atoms may independently be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (generally and specifically), and alkyloxy group substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl group substituents, and alkyloxy group substituents may be used without limitation for further description and may be used as R 2 Substituted cycloalkyl groups (general and specific).

[0207] In a non-restrictive aspect, R 2 It can be cyclohexyl, 2-alkylcyclohexyl, or 2,6-dialkylcyclohexyl; or alternatively, cyclopentyl, 2-alkylcyclopentyl, or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents may be used without limitation for further description as R. 2 The alkylcyclohexyl (generally or specifically), dialkylcyclohexyl (generally or specifically), alkylcyclopentyl (generally or specifically), and / or dialkylcyclopentyl (generally or specifically). Typically, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl may be the same; or alternatively, the alkyl substituents of the dialkylcyclohexyl or cyclopentyl may be different. In some non-limiting aspects, R 2 It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-ditert-butylcyclohexyl. In other non-limiting respects, R 2 It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl or 2-tert-butylcyclohexyl; or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-ditert-butylcyclohexyl.

[0208] On the one hand, R2 It can be phenyl, substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In one aspect, it can be used as R. 2 The substituted phenyl group can be a 2-substituted phenyl, a 3-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, a 2,6-disubstituted phenyl, a 3,5-disubstituted phenyl, or a 2,4,6-trisubstituted phenyl; alternatively, a 2-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, or a 2,6-disubstituted phenyl; alternatively, a 3-substituted phenyl or a 3,5-disubstituted phenyl; alternatively, a 2-substituted phenyl or a 4-substituted phenyl; alternatively, a 2,4-disubstituted phenyl or a 2,6-disubstituted phenyl; or alternatively, a 2,4,6-trisubstituted phenyl. In one aspect, used as R 2 One or more substituents of the polysubstituted phenyl group may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl group may be different. Each substituent of the substituted phenyl group (general or specific) may independently be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (general and specific), and alkyloxy group substituents (general and specific) are disclosed independently herein. These halogen substituents, alkyl group substituents, and alkyloxy group substituents may be used without limitation for further description and may be used as R 2 Substituted phenyl groups (general and specific).

[0209] In a non-restrictive aspect, R 2 It can be phenyl, 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-di-alkylphenyl, 2,6-dialkylphenyl, 3,5-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 4-alkylphenyl, 2,4-di-alkylphenyl, 2,6-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl or 4-alkylphenyl; alternatively, 2,4-dialkylphenyl or 2,6-dialkylphenyl; alternatively, 3-alkylphenyl or 3,5-dialkylphenyl; alternatively, 2-alkylphenyl or 2,6-dialkylphenyl; or alternatively, 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents may be used without limitation for further description as R 2Any alkyl-substituted phenyl group. Typically, the alkyl substituents of dialkylphenyl (generally or specifically) or trialkylphenyl (generally or specifically) may be the same; or alternatively, the alkyl substituents of dialkylphenyl or trialkylphenyl may be different. In some non-limiting respects, R 2 It may independently be 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.

[0210] In a non-restrictive aspect, R 2 It can be phenyl, 2-alkoxyphenyl, or 4-alkoxyphenyl. In some non-limiting aspects, R... 2 It can be phenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, 2-tert-butoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl, or 4-tert-butoxyphenyl; alternatively, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, or 2-tert-butoxyphenyl; or alternatively, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl, or 4-tert-butoxyphenyl. In another non-limiting aspect, R 2 It can be phenyl, 2-halophenyl, 4-halophenyl, or 2,6-dihalophenyl. Typically, the halides of dihalophenyl compounds can be the same; or alternatively, the halides of dihalophenyl compounds can be different. In some aspects, R... 2 It can be phenyl, 2-fluorophenyl, 4-fluorophenyl or 2,6-difluorophenyl.

[0211] On the one hand, R 2It can be benzyl or substituted benzyl; alternatively, benzyl; or alternatively, substituted benzyl. Each substituent of the substituted benzyl can independently be halogen, alkyl, or alkyloxy; alternatively, halogen or alkyl; alternatively, halogen or alkyloxy; alternatively, alkyl or alkyloxy; alternatively, halogen; alternatively, alkyl; or alternatively, alkyloxy. Halogen substituents, alkyl substituents (generally and specifically), and alkyloxy substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl substituents, and alkyloxy substituents can be used without limitation for further description and can be used as R 2 The substituted benzyl group.

[0212] In other respects, R 1 and R 2 It can be connected to form a structure containing N 2 -Oxyphosphinemidine and / or N 2 -Ophosphine-based amidine chromium compound complexes have a ring or cyclic system of carbon-nitrogen double bonds. R 1 and R 2 The connection can be specified as L 12r And it can be a suborganogroup; alternatively, a suborganogroup composed of inert functional groups; alternatively, a alkylene group; or alternatively, an alkylene group. In one aspect, L 12r Suborganogroups, when present, can be C3 to C4. 30 C3 to C 20 C3 to C 15 Or C3 to C 10 Suborganogroups. In some respects, L-groups are composed of inert functional groups. 12r Suborganogroups, when present, can be C3 to C4 groups composed of inert functional groups. 30 C3 to C 20 C3 to C 15 Or C3 to C 10 Suborganogroups. In other respects, L 12r The hydrocarbon group, when present, can independently be C3 to C4. 30 C3 to C 20 C3 to C 15 Or C3 to C 10 Hydroxyl group. In another aspect, L... 12r Alkylenes, when present, can independently be C3 to C4. 30 C3 to C 20 C3 to C 15 Or C3 to C 10 Alkylene. On the one hand, L 12rIt can be 1,3-propylidene, 1,3-butylidene, 3-methyl-1,3-butylidene (-CH2CH2C(CH3)2-), 1,4-butylidene, or 1,4-1,4-pentylidene.

[0213] Typically, the T in heterocyclic 2-[(oxophosphino)amino]imine and / or heterocyclic 2-[(oxophosphino)amino]imine chromium compound complexes can be oxygen or sulfur. On one hand, the T in heterocyclic 2-[(oxophosphino)amino]imine and / or heterocyclic 2-[(oxophosphino)amino]imine chromium compound complexes can be oxygen; or alternatively, sulfur.

[0214] Typically, having R 2a and / or R 2b N of the group 2 -Oxyphosphine guanidine and / or N 2 R of -oxophosphine-guanidine chromium compound complex 2a and / or R 2b It can be hydrogen or an organic group independently; alternatively, hydrogen or an organic group composed of inert functional groups; alternatively, hydrogen or a hydrocarbon group; alternatively, hydrogen; alternatively, an organic group; alternatively, an organic group composed of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R 2a and / or R 2b The organic group can be C1 to C2 independently. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. In some respects, R consists of inert functional groups. 2a and / or R 2b Organic groups can be independently composed of C1 to C1 inert functional groups. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. In other respects, R 2a and / or R 2b The hydrocarbon group can be independently C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 hydrocarbon groups.

[0215] On the one hand, it has R 2a and / or R 2b organic N 2 -Oxyphosphine guanidine and / or N 2 R of -oxophosphine-guanidine chromium compound complex 2a and R 2bIt may independently be an alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; alternatively, alkyl, cycloalkyl, aryl, or aralkyl; alternatively, alkyl; alternatively, substituted alkyl; alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl. In any aspect disclosed herein, R 2a and / or R 2b Alkyl groups can be independently C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, R 2a and / or R 2b Cycloalkyl groups can be independently C4 to C5. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, substituted R 2a and / or R 2b Cycloalkyl groups can be independently substituted C4 to C5 groups. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, R 2a and / or R 2b Aryl groups can be independently C6 to C6. 20 C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, the substituted R 2a and / or R 2b Aryl groups can be independently substituted C6 to C6. 20 C6 to C 15 Or C6 to C 10 Aryl. Each substituent of the substituted cycloalkyl (general or specific) / or substituted aryl (general or specific) may be halogen, alkyl, or alkyloxy; alternatively, halogen or alkyl; alternatively, halogen or alkyloxy; alternatively, alkyl or alkyloxy; alternatively, halogen; alternatively, alkyl; or alternatively, alkyloxy. Halogen substituents, alkyl substituents (general and specific), and alkyloxy substituents (general and specific) are disclosed independently herein. These halogen substituents, alkyl substituents, and alkyloxy substituents may be used without limitation for further description of R. 2a and / or R 2b .

[0216] On the one hand, N 2 -Oxyphosphine guanidine and / or N 2 R of -oxophosphine-guanidine chromium compound complex 1 and R 2a It can be linked to form the group L 12 L 12 N 1 Nitrogen atom and N 3 Nitrogen atoms form rings or ring systems. On the other hand, N... 2 -Oxyphosphine guanidine and / or N 2 R of -oxophosphine-guanidine chromium compound complex 3 and R 2b It can be linked to form the group L 23 L 23 N 2 Nitrogen atom and N 3 Nitrogen atoms form rings or ring systems. On one hand, they possess L... 12 Groups and / or L 23 N of the group 2 -Oxyphosphine guanidine and / or N 2 L-oxophosphine-guanidine chromium compound complex 12 and / or L 23 It can be an organic subgroup independently; alternatively, an organic subgroup composed of inert functional groups; or alternatively, a hydrocarbon subgroup. L 12 and / or L 23 The suborganogroup can be independently C2 to C3. 20 C2 to C 15 C2 to C 10 Or C2 to C5 suborganogroups. L composed of inert functional groups 12 and / or L 23 Suborganogroups can be independently composed of C2 to C3 inert functional groups. 20 C2 to C 15 C2 to C 10 Or C2 to C5 suborganogroups. L 12 and / or L 23 The alkylene group can be independently C2 to C3. 20 C2 to C 15 C2 to C 10 Or C2 to C5 hydrocarbon groups.

[0217] On the one hand, it has L 12 N 2 -Oxyphosphoguanidine, N 2 L-oxophosphine guanidine chromium compound complexes, heterocyclic 2-[(oxophosphine)amino]imine and / or heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes 12 and having L23 N 2 -Oxyphosphine guanidine and / or N 2 L-oxophosphine-guanidine chromium compound complex 23 It can have any of the structures provided in Table 1. In some respects, L 12 and / or L 23 It can have structures 1L, 2L, 3L, 4L, or 5L. In some aspects, L 12 and / or L 23 It can have a 2L or 3L structure; alternatively, a 4L or 5L structure. In other respects, L... 12 and / or L 23 It can have structure 1L; alternatively, structure 2L; alternatively, structure 3L; alternatively, structure 4L; or alternatively, structure 5L. In some N 2 -Oxyphosphine guanidine and N 2 Regarding α-oxophosphine-guanidine chromium compound complexes, L 12 and / or L 23 It can have a structure of 6L. It should be noted that when L... 12 or L 23 With a structure of 6L, the corresponding R 2b Or R 2a Due to N 2 -Oxyphosphine guanidine and / or N 2 N-oxyphosphine-guanidine chromium compounds 3 The nitrogen atom is connected by a double bond and is empty.

[0218] Table 1. Used for linking groups L 12 and / or L 23 The structure.

[0219]

[0220] In the structure of Table 1, L 12 and / or L 23 The unspecified valence is represented by L. 12 and / or L 23 Attached to N when it exists 2 -Oxyphosphine guanidine and N 2 The corresponding nitrogen atom of the -oxophosphine-guanidine chromium compound complex. Additionally, for the structures in Table 1, L... 12 The unspecified valence is represented by L. 12 The point of attachment to the T and corresponding nitrogen atom of the heterocyclic 2-[(oxophosphino)amino]imine and / or heterocyclic 2-[(oxophosphino)amino]imine chromium compound complex. Typically, m can be an integer ranging from 2 to 5. In other respects, m can be 2 or 3; alternatively, m can be 2; or alternatively, m can be 3. R having a linking group of structure 1LL1 and RL 2 R with a linker group having structure 2L L3 RL 4 R L5 and R L6 R with a linker group having a 3L structure L3 R L4 R L5 R L6 RL 7 and R L8 R with a linker group having structure 4L L11 and R L12 R with a linker group having a structure of 5L L23 R L24 R L25 and R L26 R with a linker group having structure 6L L27 R L28 and R L29 It can be a hydrogen or non-hydrogen substituent independently; or alternatively, hydrogen. Non-hydrogen substituents (generally and specifically) are disclosed independently herein and can be used without limitation for further description of linking groups having structure 1L, structure 2L, structure 3L, structure 4L, structure 5L and / or structure 6L. In one aspect, L 12 and / or L 23 It can independently be 1,2-vinyl (-CH2CH2-), 1,2-vinylene (-CH=CH-), 1,3-propenyl (-CH2CH2CH2-), 1-methyl-1,2-vinylene (-C(CH3)=CH-), 1,3-butenyl (-CH2CH2CH(CH3)-), 3-methyl-1,3-butenyl (-CH2CH2C(CH3)2-), or 1,2-phenylene. In some non-limiting aspects, L 12 and / or L 23 It is 1,2-vinyl (-CH2CH2-), 1,3-propenyl (-CH2CH2CH2-), 1-methyl-1,2-vinyl (-C(CH3)=CH-), 1,3-butenyl (-CH2CH2CH(CH3)-) or 3-methyl-1,3-butenyl (-CH2CH2C(CH3)2-); alternatively, 1,2-vinyl (-CH2CH2-), 1,2-vinylene (-CH=CH-), 1,3-propenyl (-CH2CH2CH2-) or 1,2-phenylene; alternatively, 1,2-vinyl (-CH2CH2-) or 1,3-propenyl (-CH2CH2CH2-); alternatively, 1,2-vinylene (-CH=CH-) or 1,2-phenylene.

[0221] On the one hand, L12 It can have a structure that includes at least one located at N 2 -Oxyphosphine guanidine and / or N 2 N-oxyphosphine-guanidine chromium compound complex 1 Substituents on the carbon atom of the nitrogen atom; alternatively, it may contain only one substituent located on the carbon atom of the nitrogen atom. 2 -Oxyphosphine guanidine and / or N 2 N-oxyphosphine-guanidine chromium compound complex 1 Substituents on the carbon atom of the nitrogen atom; or alternatively, two substituents located on the carbon atom of the nitrogen atom. 2 -Oxyphosphine guanidine and / or N 2 N-oxyphosphine-guanidine chromium compound complex 1 Substituents on the carbon atom of the nitrogen atom. On the other hand, L 12 It can have a structure that can be located at N 2 -Oxyphosphine guanidine and / or N 2 N-oxyphosphine-guanidine chromium compound complex 1 It consists of a substituent on the carbon atom of the nitrogen atom; or alternatively, it can be composed of a substituent located on the carbon atom of the nitrogen atom. 2 -Oxyphosphine guanidine and / or N 2 N-oxyphosphine-guanidine chromium compound complex 1 It consists of two substituents on the carbon atom of the nitrogen atom.

[0222] On the one hand, N 2 -Oxyphosphine guanidine and / or N 2 R of -oxophosphine-guanidine chromium compound complex 2a and R 2b It can be linked to form the group L 22 , where R 2a R 2b and N 3 Nitrogen atom (or L) 22 and N 3 Nitrogen atoms form rings or ring systems. On one hand, they possess L... 22 N of the group 2 -Oxyphosphine guanidine and / or N 2 L-oxophosphine-guanidine chromium compound complex 22 It can be a suborganogroup; alternatively, a suborganogroup composed of inert functional groups; or alternatively, a subhydrophenogroup. L 22 The suborganogroup can be C3 to C4. 20 C3 to C 15 Or C3 to C 10 Suborganogroup. L composed of inert functional groups. 22 Suborganogroups can be C3 to C4 composed of inert functional groups. 20C3 to C 15 Or C3 to C 10 Suborganogroup. L 22 The alkylene group can be C4 to C5. 20 C4 to C 15 Or C4 to C 10 Hydroxyl group.

[0223] On the one hand, L 22 It can have any of the structures provided in Table 2. In some respects, L 22 It can have structures 11L, 12L, 13L, 14L, 15L, or 16L. In other aspects, L... 22 It may have structure 11L; alternatively, structure 12L; alternatively, structure 13L; alternatively, structure 14L; or alternatively, structure 15L.

[0224] Table 2. Used for linking groups L 22 The structure.

[0225]

[0226] In the structure of Table 2, unspecified valences represent N. 2 -Oxyphosphine guanidine and / or N 2 L-oxophosphine-guanidine chromium compound complex 22 Attached to N when it exists 2 -Oxyphosphine guanidine and / or N 2 N-oxyphosphine-guanidine chromium compound complex 3 The point of the nitrogen atom. Typically, n can be an integer ranging from 4 to 7. In other respects, n can be 4 or 5; alternatively, n can be 4; or alternatively, n can be 5. R with a linking group having structure 11L. L31 and RL 32 R with a linker group of structure 12L L41 R L42 R L43 R L44 R L45 R L46 R L47 and R L48 R with a linker group of structure 13L L41 R L42 R L43 R L44 R L45 R L46 R L42 R L48 R L49 and R L50 R with a linker group of structure 14LL41 R L42 R L43 R L44 R L45 R L46 R L47 and R L48 And R with a linking group having structure 15L L41 R L42 R L43 R L44 R L45 R L46 R L47 and R L48 The substituent can be hydrogen or non-hydrogen; alternatively, hydrogen. Non-hydrogen substituents are disclosed independently herein and can be used without limitation for further description of linking groups having structures 11L, 12L, 13L, 14L, and / or 15L. In one aspect, L 22 It can be 1,4-butenyl, 1,4-pentenyl, 1,5-pentenyl, 2,5-hexenyl, 1,5-hexenyl, 2,5-heptenyl, 1,3-butadiene-1,4-ethylene or bis(eth-2-yl)ether; or alternatively, 1,4-butenyl, 1,5-pentenyl or bis(eth-2-yl)ether.

[0227] Typically, having R 3 N of the group 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphinemidine, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphoguanidine, N 2 R of -oxophosphine-guanidinium chromium compound complexes, heterocyclic 2-[(oxophosphine)amino]imine and / or heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes 3 It can be hydrogen or an organic group; hydrogen or an organic group composed of inert functional groups; alternatively, hydrogen or a hydrocarbon group; alternatively, hydrogen; alternatively, an organic group; alternatively, an organic group composed of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R 3 The organic group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On the one hand, R is composed of inert functional groups. 3 Organic groups can be C1 to C1 composed of inert functional groups. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On one hand, R3 The hydrocarbon group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 hydrocarbon groups. In other respects, it has R... 3 N of the group 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphinemidine, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphoguanidine, N 2 R of -oxophosphine-guanidinium chromium compound complexes, heterocyclic 2-[(oxophosphine)amino]imine and / or heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes 3 It can be C1 to C 30 C1 to C 20 C1 to C 15 C1 to C 10 Or C1 to C5 alkyl. In other respects, N 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphinemidine, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphoguanidine, N 2 R of -oxophosphine-guanidinium chromium compound complexes, heterocyclic 2-[(oxophosphine)amino]imine and / or heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes 3 It can be phenyl or substituted C6 to C3. 20 Phenyl; alternatively, phenyl or substituted C6 to C6. 15 Phenyl; or alternatively, phenyl or substituted C6 to C6. 10 Phenyl. Substituents (general and specific) are provided herein and these substituents can be used for further description as having non-hydrogen R. 3 N of the group 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphinemidine, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphine guanidine and / or N 2 R of -oxophosphine-guanidine chromium compound complex 3 The substituted phenyl group.

[0228] Typically, N 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2-Oxyphosphinemidine, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphoguanidine, N 2 R of -oxophosphine-guanidinium chromium compound complexes, heterocyclic 2-[(oxophosphine)amino]imine and / or heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes 4 and / or R 5 It can be an organic group independently; alternatively, an organic group composed of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R... 4 and / or R 5 The organic group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On the one hand, R is composed of inert functional groups. 4 and / or R 5 Organic groups can be C1 to C1 composed of inert functional groups. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On one hand, R 4 and / or R 5 The hydrocarbon group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 hydrocarbon groups. On the one hand, N 2 -Oxyphosphine formamidin, N 2 -Oxyphosphine-formamidinium chromium compound complex, N 2 -Oxyphosphinemidine, N 2 -Oxyphosphine-based amidine chromium compound complex, N 2 -Oxyphosphoguanidine, N 2 R of -oxophosphine-guanidinium chromium compound complexes, heterocyclic 2-[(oxophosphine)amino]imine and / or heterocyclic 2-[(oxophosphine)amino]imine chromium compound complexes 4 and / or R 5 It may be independently an alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; alternatively, alkyl, cycloalkyl, aryl or aralkyl; alternatively, alkyl; alternatively, substituted alkyl; alternatively, cycloalkyl; alternatively, substituted cycloalkyl; alternatively, aryl; alternatively, substituted aryl; alternatively, aralkyl; or alternatively, substituted aralkyl.

[0229] In any respect disclosed herein, R4 and / or R 5 Alkyl groups can be independently C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, substituted R 4 and / or R 5 Alkyl groups can be independently substituted C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, R 4 and / or R 5 Cycloalkyl groups can be independently C4 to C5. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, substituted R 4 and / or R 5 Cycloalkyl groups can be independently substituted C4 to C5 groups. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, R 4 and / or R 5 Aryl groups can be independently C6 to C6. 20 C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, the substituted R 4 and / or R 5 Aryl groups can be independently substituted C6 to C6. 20 C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, R 4 and / or R 5 Aryl groups can be independently C7 to C8. 20 C7 to C 15 Or C7 to C 10 Aryl alkyl groups. In any respect disclosed herein, substituted R 4 and / or R 5 Aryl groups can be independently substituted C7 to C8. 20 C7 to C 15 Or C7 to C 10Arane. Each substituent of the substituted alkyl (general or specific), substituted cycloalkyl (general or specific), substituted aryl (general or specific), and / or substituted arane (general or specific) may be halogen, alkyl, or alkyloxy; alternatively, halogen or alkyl; alternatively, halogen or alkyloxy; alternatively, alkyl or alkyloxy; alternatively, halogen; alternatively, alkyl; or alternatively, alkyloxy. Halogen substituents, alkyl substituents (general and specific), and alkyloxy substituents (general and specific) are disclosed independently herein. These halogen substituents, alkyl substituents, and alkyloxy substituents may be used without limitation for further description of R. 4 and / or R 5 .

[0230] On the one hand, R 4 and R 5 It can be independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; or alternatively, methyl, ethyl, n-propyl (1-propyl), isopropyl (2-propyl), 2-methyl-1-propyl, tert-butyl (2-methyl-2-propyl), or neopentyl (2,2-dimethyl-1-propyl). In some respects, it can be used as R. 4 and / or R 5 The alkyl group can be substituted. Each substituent of the substituted alkyl group can independently be a halogen or an alkyloxy group; alternatively, a halogen; or alternatively, an alkyloxy group. Halogen substituents and alkyl substituents (general and specific) are disclosed independently herein. These halogen and alkyloxy substituents can be used without limitation for further description and can be used as R 4 and / or R 5 Substituted alkyl groups.

[0231] On the one hand, R 4 and R 5 It can be independently cyclopentyl, substituted cyclopentyl, cyclohexyl, or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; or alternatively, cyclohexyl or substituted cyclohexyl. In one aspect, it can be used for R 4 and / or R 5The substituted cycloalkyl group can be a 2-substituted cyclohexyl, a 2,6-disubstituted cyclohexyl, a 2-substituted cyclopentyl, or a 2,5-disubstituted cyclopentyl; alternatively, a 2-substituted cyclohexyl or a 2,6-disubstituted cyclohexyl; alternatively, a 2-substituted cyclopentyl or a 2,5-disubstituted cyclopentyl; alternatively, a 2-substituted cyclohexyl or a 2-substituted cyclopentyl; or alternatively, a 2,6-disubstituted cyclohexyl or a 2,5-disubstituted cyclopentyl. In respect of the substituted cycloalkyl group (generally or specifically) having more than one substituent, the substituents can be the same or different; alternatively, the same; or alternatively, different. Each substituent of a cycloalkyl group having a specified number of cyclic carbon atoms (generally or specifically) may independently be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, alkyl group or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (generally and specifically), and alkyloxy group substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl group substituents, and alkyloxy group substituents may be used without limitation for further description and may be used as R 4 and / or R 5 Substituted cycloalkyl groups (general and specific).

[0232] In a non-restrictive aspect, R 4 and R 5 Alkyl substituents can be cyclohexyl, 2-alkylcyclohexyl, or 2,6-dialkylcyclohexyl independently; or alternatively, cyclopentyl, 2-alkylcyclopentyl, or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents may be used without limitation in further description as R. 4 and / or R 5 The alkylcyclohexyl (generally or specifically), dialkylcyclohexyl (generally or specifically), alkylcyclopentyl (generally or specifically), and / or dialkylcyclopentyl (generally or specifically). Typically, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl may be the same; or alternatively, the alkyl substituents of the dialkylcyclohexyl or cyclopentyl may be different. In some non-limiting aspects, R 4 and R 5 It can independently be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-ditert-butylcyclohexyl. In other non-limiting respects, R 4 and R 5It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl or 2-tert-butylcyclohexyl independently; or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-ditert-butylcyclohexyl.

[0233] On the one hand, R 4 and R 5 It can be phenyl independently, a substituted phenyl; alternatively, phenyl; or alternatively, a substituted phenyl. In one aspect, it can be used for R 4 and / or R 5 The substituted phenyl group can be a 2-substituted phenyl, a 3-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, a 2,6-disubstituted phenyl, a 3,5-disubstituted phenyl, or a 2,4,6-trisubstituted phenyl; alternatively, a 2-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, or a 2,6-disubstituted phenyl; alternatively, a 3-substituted phenyl or a 3,5-disubstituted phenyl; alternatively, a 2-substituted phenyl or a 4-substituted phenyl; alternatively, a 2,4-disubstituted phenyl or a 2,6-disubstituted phenyl; or alternatively, a 2,4,6-trisubstituted phenyl. In one aspect, used as R 4 and / or R 5 One or more substituents of the polysubstituted phenyl group may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl group may be different. Each substituent of the substituted phenyl group (general or specific) may independently be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (general and specific) and alkyloxy group substituents (general and specific) are disclosed independently herein. These halogen substituents, alkyl group substituents, and alkyloxy group substituents may be used without limitation for further description of the substituted phenyl group (general and specific) that may be used as R4 and / or R5.

[0234] In a non-restrictive aspect, R 4 and R 5It can be independently phenyl, 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, 3,5-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl or 4-alkylphenyl; alternatively, 2,4-dialkylphenyl or 2,6-dialkylphenyl; alternatively, 3-alkylphenyl or 3,5-dialkylphenyl; alternatively, 2-alkylphenyl or 2,6-dialkylphenyl; or alternatively, 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents can be used without limitation to further describe any alkyl-substituted phenyl that can be used as R4 and / or R5. Typically, the alkyl substituents of dialkylphenyl (generally or specifically) or trialkylphenyl (generally or specifically) may be the same; or alternatively, the alkyl substituents of dialkylphenyl (generally or specifically) or trialkylphenyl (generally or specifically) may be different. In some non-limiting aspects, R 4 and R 5 It may independently be 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.

[0235] In a non-restrictive aspect, R 4 and R 5 It can be phenyl, 2-alkoxyphenyl, or 4-alkoxyphenyl. In some non-limiting aspects, R... 4 and / or R 5 It can be phenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, 2-tert-butoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl, or 4-tert-butoxyphenyl; alternatively, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, or 2-tert-butoxyphenyl; or alternatively, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl, or 4-tert-butoxyphenyl. In a non-limiting aspect, R 4 and R 5It can be independently phenyl, 2-halophenyl, 4-halophenyl, or 2,6-dihalophenyl. Typically, the halides of dihalophenyl compounds can be the same; or alternatively, the halides of dihalophenyl compounds can be different. In some respects, R... 4 and R 5 It can be phenyl, 2-fluorophenyl, 4-fluorophenyl or 2,6-difluorophenyl independently.

[0236] On the one hand, R 4 and R 5 The substituent may be independently benzyl or substituted benzyl; alternatively, benzyl; or alternatively, substituted benzyl. Each substituent of the substituted benzyl may be independently halogen, alkyl, or alkyloxy; alternatively, halogen or alkyl; alternatively, halogen or alkyloxy; alternatively, alkyl or alkyloxy; alternatively, halogen; alternatively, alkyl; or alternatively, alkyloxy. Halogen substituents, alkyl substituents (generally and specifically), and alkyloxy substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl substituents, and alkyloxy substituents may be used without limitation for further description and may be used as R 4 and / or R 5 The substituted benzyl group.

[0237] In other respects, R 4 and R 5 They can be linked to form rings or ring systems containing phosphorus atoms. R 4 and R 5 The connection can be specified as L 45 And it can be a suborganogroup; alternatively, a suborganogroup composed of inert functional groups; alternatively, a subalkyl group; or alternatively, an alkylene group. In one aspect, L 45 Suborganogroups, when present, can be C4 to C5. 30 C4 to C 20 C4 to C 15 Or C4 to C 10 Suborganogroups. On one hand, L-shaped groups composed of inert functional groups. 45 Suborganogroups, when present, can be C4 to C5 groups composed of inert functional groups. 30 C4 to C 20 C4 to C 15 Or C4 to C 10 Suborganogroups. On the one hand, L 45 The hydrocarbon group, when present, can independently be C4 to C5. 30 C4 to C 20 C4 to C 15 Or C4 to C 10 Hydroxyl group. In another aspect, L... 45Alkylenes, when present, can independently be C4 to C5. 30 C4 to C 20 C4 to C 15 Or C4 to C 10 Alkylene. On the one hand, L 45 It can be 1,4-butenyl, 1,4-diphenyl-1,4-butenyl, 1,4-di(2-methylphenyl)-1,4-butenyl, 1,4-di(4-methylphenyl)-1,4-butenyl, 1,4-di(4-tert-butylphenyl)-1,4-butenyl, 1,4-di(3,5-dimethylphenyl)-1,4-butenyl, 1,4-pentenyl, 1-phenyl-1,4-pentenyl, 4-phenyl-1,4-pentenyl, 2,5-hexenyl, 2,2'-biphenylene, 2,2'-(methanediyl)diphenylene, or 2,2'-(1,2-ethanediyl)diphenylene.

[0238] On the one hand, heteroatom ligands or heteroatom ligand chromium compound complexes may have the following formula (R 1s ) m X 1s (L 1s )X 2s (R 2s )n, while heteroatom ligand chromium compound complexes can have the following formula:

[0239]

[0240] In some respects, heteroatom ligands or heteroatom ligand chromium compound complexes may have heteroatom ligands that can be used with formula (R 1s ) m X 1s (L 1s )X 2s (R 2s ) n The two groups described. In heteroatom ligands, there can be groups that can be represented by formula (R). 1s ) m X 1s (L 1s )X 2s (R 2s ) n In the case of the two groups described, the two L 1s Group linkages and heteroatom ligands and heteroatom ligand chromium compound complexes can each have the following formulas:

[0241]

[0242] In having the formula (R) 1s ) m X 1s (L 1s )X2s (R 2s ) n Or has two connections (R) 1s ) m X 1s (L 1s )X 2s (R 2s ) n In the heteroatom ligands of the group or the heteroatom ligands of the chromium compound complex, each X 1s and each X 2s It can be independently selected from N, P, O, and S; each L 1s It can be the corresponding X 1s s and X 2s Independent linking groups between s; each m and each n can be independently 1 or 2; and each R 1s and each R 2s It can be hydrogen, an organogroup (or alternatively, an organogroup composed of inert functional groups; or alternatively, a hydrocarbon group) or a heterohydrogroup, wherein when two or more R groups are present... 1s and / or two Rs 2s At that time, each R 1s They can be the same or different (or alternatively, the same; or alternatively, different) and / or each R 2s They can be the same or different (or alternatively, the same; or alternatively, different). L 1s X 1s X 2s R 1s R 2s m and n are L 1s X 1s X 2s R 1s R 2s The independent elements of any heteroatom ligand, m, and / or n, or any heteroatom ligand in a chromium compound complex, are described independently herein. 1s X 1s X 2s R 1s R 2s These independent descriptions of m and n can be used without restriction in any combination to further describe L 1s X 1s X 2s R 1s R 2s Any heteroatom ligand of m and / or n, or any heteroatom ligand of a chromium compound complex. Additionally, CrX pIt is an independent element of the heteroatom ligand chromium compound complex and is described independently herein, and can be used without restriction with the L heteroatom ligand. 1s X 1s X 2s R 1s R 2s m and n are used in any combination to further describe the heteroatom ligand chromium compound complexes considered herein.

[0243] On the one hand, the X described in this article 1s and / or X 2s For each X of any heteroatom ligand or any heteroatom ligand chromium compound complex, there is no heteroatom ligand. 1s and each X 2s It can be independently selected from N, P, O, and S; alternatively, it can be independently selected from N and P; or alternatively, it can be independently selected from O and S. In some respects, each X 1s and each X 2s It can be N; alternatively, P; alternatively, O; or alternatively, S. Each m and each n of any heteroatom ligand having m and / or n, or any heteroatom ligand in any heteroatom ligand chromium compound complex, described herein can be independently selected from 1 or 2; alternatively, 1; or alternatively, 2. In some particular aspects, when X 1s and / or X 2s They are either O or S; alternatively, it is O; or alternatively, when it is S, each m and / or each n can be 1. In some other specific respect, when X 1s and / or X 2s When the values ​​are N or P, it is alternatively N; or alternatively, when the values ​​are P, each m and / or each n can be 2.

[0244] In a non-restrictive aspect, heteroatom ligands can have the following 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 Alternatively, (R) 1s )2P(L 1s )P(R 2s )2; or alternatively, (R 1s )2N(L 1s )N(R2s )2, while heteroatom ligand chromium compound complexes can have any of the following formulas:

[0245] and / or

[0246] In a non-restrictive sense, the heteroatom ligand or heteroatom ligand chromium compound complex may have two linked heteroatom groups, and the heteroatom ligand may have one or more of the following formulas:

[0247] and / or

[0248] The heteroatom ligand chromium compound complex can have any of the following formulas:

[0249] and / or

[0250] In one respect, each L of any heteroatom ligand or heteroatom ligand chromium compound complex described herein is a heteroatom ligand. 1s It can independently be a group capable of connecting X 1s and X 2s Any group (and when more than one L) 1s At that time, it is another L of heteroatom ligands in heteroatom ligand or heteroatom ligand chromium compound complexes. 1s (Groups). In some respects, each L 1s It can be an organic subgroup, an amine-dimethyl group, or a phosphine-dimethyl group independently; alternatively, it can be an organic subgroup, an amine-dimethyl group, or a phosphine-dimethyl group composed of inert functional groups; alternatively, it can be an alkylene group, an amine-dimethyl group, or a phosphine-dimethyl group; alternatively, it can be an amine-dimethyl group or a phosphine-dimethyl group; alternatively, it can be an organic subgroup; alternatively, it can be an organic subgroup composed of inert functional groups; alternatively, it can be an alkylene group; alternatively, it can be an amine-dimethyl group; or alternatively, it can be a phosphine-dimethyl group. When more than one L is present in the heteroatom ligand or the heteroatom ligand chromium compound complex. 1s When groups are present, each L 1s It can be an organic group, an amino group, or a phosphine group independently; alternatively, an organic group, an amino group, or a phosphine group composed of inert functional groups; alternatively, a hydrocarbon group, an amino group, or a phosphine group; alternatively, an amino group or a phosphine group; alternatively, an organic group; alternatively, an organic group composed of inert functional groups; alternatively, a hydrocarbon group; alternatively, an amino group; or alternatively, a phosphine group. In one aspect, L 1s The suborganogroup or organic group can be C1 to C1. 20 C1 to C 15 C1 to C 10Or C1 to C5 suborganogroups or organic groups. On one hand, L-shaped groups composed of inert functional groups... 1s Suborganogroups can be C1 to C1 composed of inert functional groups. 20 C1 to C 15 C1 to C 10 Or C1 to C5 suborganogroups or organic groups. On one hand, L 1s The alkylene group can be C1 to C2. 20 C1 to C 15 C1 to C 10 It can be a C1 to C5 alkylene group or a hydrocarbon group. On one hand, the amine-dimethyl or amine group can be C1 to C5. 30 C1 to C 20 C1 to C 15 Or C1 to C 10 Amino-dimethyl or amino group. On one hand, the phosphine-dimethyl or phosphine group can be C1 to C2. 30 C1 to C 20 C1 to C 15 Or C1 to C 10 Phosphine-diyl or phosphine-based.

[0251] On the one hand, each L 1s Suborganogroups or organic groups can have 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 one respect, each amine-dimer can have the formula -N(R) 5s In one respect, each phosphine-dimethyl group can have the formula -P(R). 5s )-。 In these L 1s In the formula of the group, the dash indicates the v of the heteroatom ligand of the heteroatom ligand or heteroatom ligand chromium compound complex described herein. 1s and X 2s The attached unspecified valence. When more than one L exists in the heteroatom ligand or the heteroatom ligand of the chromium compound complex. 1s When groups are present, each L 1s R of the group 5s It can be combined to specify L 2sThe linking group. In some non-limiting aspects, the heteroatom ligand may have the structure PNP1, structure PNP2, structure NRNRN, structure PRPRP, structure SRNRS, structure PRNRP, and structure NRPRN; alternatively, structure PNP1 or structure PNP2; alternatively, structure PRPRP, structure SRNRS, or structure PRNRP; alternatively, structure PNP1; alternatively, structure PNP2; alternatively, structure NRNRN; alternatively, structure PRPRP; alternatively, structure SRNRS; alternatively, structure PRNRP; or alternatively, structure NRPRN. In some non-limiting aspects, heteroatom ligands (R...) can be used in the catalyst system described herein. 1s ) m X 1s (L 1s )X 2s (R 2s ) n The heteroatom ligand chromium compound complex may have the structures PNPCr-1, PNPCr-2, NNRNCr-1, PRPRPC-1r, SRNRSCr-1, PRNRPC-1r, and NRPRNCr-1; alternatively, PNPCr-1 or PNPCr-2; alternatively, PRPRPCr-1, SRNRSCr-1, or PRNRPC-1r; alternatively, PNPCr-1; alternatively, PNPCr-2; alternatively, NRNRNC-1r; alternatively, PRPRPCr-1; alternatively, SRNRSCr-1; alternatively, PRNRPCr-1; or alternatively, NRPRNC-1r.

[0252]

[0253] R 5s L 2s L 3s L 4s R 11s R 12s R 13s and R 14sEach is an independent element of a heteroatom ligand having the structure PNP-1, PNP-2, NRNRN-1, PPRRP-1, SRNRS-1, PRNRP-1, or NRPRN-1, and / or heteroatom ligands of chromium compound complexes having the structures PNPCr-1, PNPCr-2, NNRNRNCr-1, PPRPCr-1, SRNRS-1, PRNRP-1, and NNRPRNCr-1 (which appear therein and are described independently). R 5s L 2s L 3s L 4s R 11s R 12s R 13s and R 14s The independent descriptions of X and p can be used without limitation in any combination to further describe the heteroatom ligand structures and / or heteroatom ligand chromium compound complex structures in which they appear. Similarly, X and p are independent elements of heteroatom ligand chromium compound complexes having structures PNPCr-1, PNPCr-2, NNRNCr-1, PPRPCr-1, SRRNSCr-1, PPRPCr-1, and NRPRNCr-1, and are described independently herein. The independent descriptions of X and p can be used without limitation in conjunction with the independent descriptions of R provided herein. 5s L 2s L 3s L 4s R 11s R 12s R 13s and R 14s Any combination thereof may be used to further describe any heteroatom ligand chromium compound complex having structure PNPCr-1, structure PNPCr-2, structure NNRNCr-1, structure PRPRPCr-1, structure SRNRSCr-1, structure PRNRPCr-1 and / or structure NRPRNCr-1.

[0254] Typically, having R 1s R 2s R 11s R 12s R 13s and / or R 14s The R group of any heteroatom ligand structure described herein and / or any heteroatom ligand chromium compound complex described herein 1s R 2s R 11s R 12s R 13s and / or R14s It can be an organic group independently; alternatively, an organic group composed of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, it can be used as R. 1s R 2s R 11s R 12s R 13s and / or R 14s The organogroup can be independently C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On one hand, it can be used as R... 1s R 2s R 11s R 12s R 13s and / or R 14s Organic groups composed of inert functional groups can be C1 to C1 groups composed of inert functional groups. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organic groups. On one hand, it can be used as R... 1s R 2s R 11s R 12s R 13s and / or R 14s The hydrocarbon group can be independently C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 hydrocarbon groups.

[0255] On the one hand, it has R 1s R 2s R 11s R 12s R 13s and / or R 14s The R group of any heteroatom ligand structure described herein and / or any heteroatom ligand chromium compound complex described herein 1s R 2s R 11s R 12s R 13s and / or R 14s It may independently be an alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; alternatively, alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; or alternatively, alkyl, cycloalkyl, aryl, or aralkyl. In other respects, having R 1s R2s R 11s R 12s R 13s and / or R 14s For each R group of any heteroatom ligand structure described herein and / or any heteroatom ligand chromium compound complex described herein 1s R 2s R 11s R 12s R 13s and / or R 14s It may be an alkyl group independently; 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.

[0256] In any respect disclosed herein, each R 1s R 2s R 11s R 12s R 13s and / or R 14s Alkyl groups can be independently C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, each substituted R 1s R 2s R 11s R 12s R 13s and / or R 14s Alkyl groups can be independently substituted C1 to C2. 20 C1 to C 10 Or C1 to C5 alkyl. In any respect disclosed herein, each R... 1s R 2s R 11s R 12s R 13s and / or R 14s Cycloalkyl groups can be independently C4 to C5. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, each substituted R 1s R 2s R 11s R 12s R 13s and / or R 14s Cycloalkyl groups can be independently substituted C4 to C5 groups. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, each R...1s R 2s R 11s R 12s R 13s and / or R 14s Aryl groups can be independently C6 to C6. 20 C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, each substituted R 1s R 2s R 11s R 12s R 13s and / or R 14s Aryl groups can be independently substituted C6 to C6. 20 C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, each R 1s R 2s R 11s R 12s R 13s and / or R 14s Aryl groups can be independently C7 to C8. 20 C7 to C 15 Or C7 to C 10 Aryl alkyl. In any respect disclosed herein, each substituted R... 1s R 2s R 11s R 12s R 13s and / or R 14s Aryl groups can be independently substituted C7 to C8. 20 C7 to C 15 Or C7 to C 10 Araneyl groups. Each substituent of a substituted alkyl group (generally or specifically), a substituted cycloalkyl group (generally or specifically), a substituted aryl group (generally or specifically), and / or a substituted araneyl group (generally or specifically) may be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, alkyl group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (generally and specifically), and alkyloxy group substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyloxy group substituents, and alkyloxy group substituents may be used without limitation for further description and may be used as R 1s R 2s R 11s R 12s R 13s and / or R 14sSubstituted groups (general or specific).

[0257] On the one hand, each R 1s R 2s R 11s R 12s R 13s and / or R 14s It can be independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; or alternatively, methyl, ethyl, isopropyl (2-propyl), tert-butyl (2-methyl-2-propyl), or neopentyl (2,2-dimethyl-1-propyl). In some respects, it can be used as each R 1s R 2s R 11s R 12s R 13s and / or R 14s The alkyl group can be substituted independently. Each substituent of the substituted alkyl group can be independently halogenated or alkyloxylated; alternatively, halogenated; or alternatively, alkyloxylated. Halogenated substituents and alkyl substituents (general and specific) are disclosed independently herein. These halogenated and alkyloxy substituents can be used without limitation for further description and can be used as R 1s R 2s R 11s R 12s R 13s and / or R 14s Substituted alkyl groups (general or specific).

[0258] On the one hand, each R 1s R 2s R 11s R 12s R 13s and / or R 14s It can be independently cyclopentyl, substituted cyclopentyl, cyclohexyl, or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; alternatively, cyclohexyl or substituted cyclohexyl; alternatively, cyclopentyl; alternatively, substituted cyclopentyl; alternatively, cyclohexyl; or alternatively, substituted cyclohexyl. In one aspect, it can be used in R when present in any heteroatom ligand described herein, any heteroatom ligand of the heteroatom ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or any heteroatom ligand chromium compound complex structure provided herein. 1s R 2s R 11s R 12s R 13s and / or R 14sThe substituted cycloalkyl group in any of these can independently be a 2-substituted cyclohexyl, a 2,6-disubstituted cyclohexyl, a 2-substituted cyclopentyl, or a 2,5-disubstituted cyclopentyl; alternatively, a 2-substituted cyclohexyl or a 2,6-disubstituted cyclohexyl; alternatively, a 2-substituted cyclopentyl or a 2,5-disubstituted cyclopentyl; alternatively, a 2-substituted cyclohexyl or a 2-substituted cyclopentyl; or alternatively, a 2,6-disubstituted cyclohexyl or a 2,5-disubstituted cyclopentyl. In one aspect, used as R 1s R 2s R 11s R 12s R 13s and / or R 14s One or more substituents of the polysubstituted cycloalkyl group may be the same or different; alternatively, all substituents of the polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of the polysubstituted cycloalkyl group may be different. Each substituent of the substituted cycloalkyl group (generally or specifically) having a specified number of ring carbon atoms may independently be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (generally and specifically), and alkyloxy group substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl group substituents, and alkyloxy group substituents may be used without limitation for further description and may be used as R 1s R 2s R 11s R 12s R 13s and / or R 14s Substituted cycloalkyl groups (general or specific).

[0259] In a non-restrictive aspect, each R 1s R 2s R 11s R 12s R 13s and / or R 14s Alkyl substituents can be cyclohexyl, 2-alkylcyclohexyl, or 2,6-dialkylcyclohexyl independently; or alternatively, cyclopentyl, 2-alkylcyclopentyl, or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents may be used without limitation in further description as R. 1s R 2s R 11s R 12s R 13s and / or R 14The alkylcyclohexyl (generally or specifically), dialkylcyclohexyl (generally or specifically), alkylcyclopentyl (generally or specifically), and / or dialkylcyclopentyl (generally or specifically). Typically, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl may be the same; or alternatively, the alkyl substituents may be different. In some non-limiting aspects, each R... 1s R 2s R 11s R 12s R 13s and R 14s It can be independently 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl or 2,6-ditert-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-ditert-butylcyclohexyl.

[0260] On the one hand, each R 1s R 2s R 11s R 12s R 13s and / or R 14s It may be independently phenyl or substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In one aspect, it may be used in each R when present in any heteroatom ligand described herein, any heteroatom ligand of the heteroatom ligand chromium compound complex described herein, any heteroatom ligand formula or structure provided herein, and / or any heteroatom ligand chromium compound complex structure provided herein. 1s R 2s R 11s R 12s R 13s and / or R 14sThe substituted phenyl group can independently be a 2-substituted phenyl, a 3-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, a 2,6-disubstituted phenyl, a 3,5-disubstituted phenyl, or a 2,4,6-trisubstituted phenyl; alternatively, a 2-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, or a 2,6-disubstituted phenyl; alternatively, a 3-substituted phenyl or a 3,5-disubstituted phenyl; alternatively, a 2-substituted phenyl or a 4-substituted phenyl; alternatively, a 2,4-disubstituted phenyl or a 2,6-disubstituted phenyl; alternatively, a 2-substituted phenyl; alternatively, a 3-substituted phenyl; alternatively, a 4-substituted phenyl; alternatively, a 2,4-disubstituted phenyl; alternatively, a 2,6-disubstituted phenyl; alternatively, a 3,5-disubstituted phenyl; or alternatively, a 2,4,6-trisubstituted phenyl. In one aspect, used as R 1s R 2s R 11s R 12s R 13s and / or R 14s One or more substituents of the polysubstituted phenyl group may be the same or different; alternatively, all substituents may be the same; or alternatively, all substituents may be different. Each substituent of the substituted phenyl group (generally or specifically) may independently be halogen, alkyl, or alkyloxy; alternatively, halogen or alkyl; alternatively, halogen or alkyloxy; alternatively, alkyl or alkyloxy; alternatively, halogen; alternatively, alkyl; or alternatively, alkyloxy. Halogen substituents, alkyl substituents (generally and specifically), and alkyloxy substituents (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl substituents, and alkyloxy substituents may be used without limitation for further description and may be used as R 1s R 2s R 11s R 12s R 13s and / or R 14s The substituted phenyl group (general or specific).

[0261] In a non-restrictive aspect, each R 1s R 2s R 11s R 12s R 13s and / or R 14sAlkyl substituents may independently be phenyl, 2-alkylphenyl, 3-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, 3,5-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl or 4-alkylphenyl; alternatively, 2,4-dialkylphenyl or 2,6-dialkylphenyl; alternatively, 3-alkylphenyl or 3,5-dialkylphenyl; alternatively, 2-alkylphenyl or 2,6-dialkylphenyl; or alternatively, 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents may be used without limitation for further description as R 1s R 2s R 11s R 12s R 13s and / or R 14s Any alkyl-substituted phenyl group. Typically, the alkyl substituents of dialkylphenyl (general or specific) or trialkylphenyl (general or specific) may be the same; or alternatively, the alkyl substituents may be different. In some non-limiting aspects, each R... 1s R 2s R 11s R 12s R 13a and / or R 14s It may independently be 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.

[0262] In a non-restrictive aspect, each R 1s R 2s R 11 s, R 12s R 13sand / or R 14s It can be phenyl, 2-alkoxyphenyl, or 4-alkoxyphenyl independently. In some non-limiting aspects, each R... 1s R 2s R 11s R 12s R 13s and / or R 14s It may independently be phenyl, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, 2-tert-butoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl, or 4-tert-butoxyphenyl; alternatively, 2-methoxyphenyl, 2-ethoxyphenyl, 2-isopropoxyphenyl, or 2-tert-butoxyphenyl; or alternatively, 4-methoxyphenyl, 4-ethoxyphenyl, 4-isopropoxyphenyl, or 4-tert-butoxyphenyl. In a non-limiting aspect, each R 1s R 2s R 11s R 12s R 13s and / or R 14s It can be independently phenyl, 2-halophenyl, 4-halophenyl, or 2,6-dihalophenyl. Typically, the halides of dihalophenyl compounds can be the same, or alternatively, the halides can be different. In some aspects, each R... 1s R 2s R 11s R 12s R 13s and / or R 14s It can be phenyl, 2-fluorophenyl, 4-fluorophenyl or 2,6-difluorophenyl independently.

[0263] On the one hand, each R 1s R 2s R 11s R 12s R 13s and / or R 14scan independently be benzyl or substituted benzyl; alternatively, benzyl; or alternatively, substituted benzyl. Each substituent of the (general or specific) substituted benzyl can independently be a halogen, a hydrocarbyl group, or a hydrocarbyloxy group; alternatively, a halogen or a hydrocarbyl group; alternatively, a halogen or a hydrocarbyloxy group; alternatively, a hydrocarbyl group or a hydrocarbyloxy group; alternatively, a halogen; alternatively, a hydrocarbyl group; or alternatively, a hydrocarbyloxy group. Halogen substituents, hydrocarbyl substituents (general and specific), and hydrocarbyloxy substituents (general and specific) are independently disclosed herein. These halogen substituents, hydrocarbyl substituents, and hydrocarbyloxy substituents can be used without limitation to further describe the R 1s , R 2s , R 11s , R 12s , R 13s and / or R 14s substituted benzyl (general or specific).

[0264] In other respects, two geminal R 1s , two geminal R 2s , the geminal R 11s and R 12s and / or the geminal R 13s and R 14s can independently be connected to form a ring or ring system containing the heteroatom to which they are attached. The linkage of the two geminal R 1s can be designated as L 11s . The linkage of the two geminal R 2s can be designated as L 22s . The linkage of the geminal R 11s and R 12s can be designated as L 12s . The linkage of the geminal R 13s and R 14s can be designated as L 34s . In one aspect, L 11s , L 22s , L 12s and / or L 34s can independently be a divalent organic group; alternatively, a divalent organic group consisting of an inert functional group; alternatively, a divalent hydrocarbyl group; or alternatively, an alkylene group. In one aspect, L 11s , L 22s , L 12s and / or L 34s the divalent organic group, when present, can independently be a C4 to C 30 , C4 to C 20 , C4 to C 15 or C4 to C 10 divalent organic group. In some aspects, the L consisting of an inert functional group 11s , L 22s , L 12sand / or L 34s Suborganogroups, when present, can independently be composed of C4 to C5 inert functional groups. 30 C4 to C 20 C4 to C 15 Or C4 to C 10 Suborganogroups. In other respects, L 11s L 22s L 12s and / or L 34s The hydrocarbon group, when present, can independently be C4 to C5. 30 C4 to C 20 C4 to C 15 Or C4 to C 10 Hydroxyl group. In another aspect, L... 11s L 22s L 12s and / or L 34s Alkylenes, when present, can independently be C4 to C5. 30 C4 to C 20 C4 to C 15 Or C4 to C 10 Alkylene. On the one hand, L 12s and / or L 34s When present, it can be independently 1,4-butenyl, 1,4-diphenyl-1,4-butenyl, 1,4-di(2-methylphenyl)-1,4-butenyl, 1,4-di(4-methylphenyl)-1,4-butenyl, 1,4-di(4-tert-butylphenyl)-1,4-butenyl, 1,4-di(3,5-dimethylphenyl)-1,4-butenyl, 1,4-pentenyl, 1-phenyl-1,4-pentenyl, 4-phenyl-1,4-pentenyl, 2,5-hexenyl, 2,2'-biphenylene, 2,2'-(methanediyl)diphenylene, or 2,2'-(1,2-ethanediyl)diphenylene.

[0265] Typically, having R 5s The R group of any heteroatom ligand structure described herein and any heteroatom ligand chromium compound complex described herein 5s It can be an organic group; alternatively, an organic group composed of inert functional groups; or alternatively, a hydrocarbon group. In one aspect, R... 5s The organic group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 organogroups. On one hand, R5s organogroups composed of inert functional groups can be C1 to C5 organogroups composed of inert functional groups. 20 C1 to C 15 C1 to C 10Or C1 to C5 organic groups. On one hand, R 5s The hydrocarbon group can be C1 to C2. 20 C1 to C 15 C1 to C 10 Or C1 to C5 hydrocarbon groups.

[0266] On the one hand, it has R 5s The R group of any heteroatom ligand structure described herein and any heteroatom ligand chromium compound complex described herein 5s It can be alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, aralkyl, or substituted aralkyl; it can be alkyl or substituted alkyl; alternatively, cycloalkyl or substituted cycloalkyl; alternatively, aryl or substituted aryl; alternatively, aralkyl or substituted aralkyl; or alternatively, alkyl, cycloalkyl, aryl, or aralkyl. In other respects, having R 5s The R group of any heteroatom ligand structure described herein and any heteroatom ligand chromium compound complex described herein 5s It can 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. In any respect disclosed herein, R 5s Alkyl groups can be C1 to C2. 20 C1 to C 15 Or C1 to C 10 Alkyl. In any respect disclosed herein, substituted R 5s Alkyl groups can be substituted C1 to C2. 20 C1 to C 15 Or C1 to C 10 Alkyl. In any respect disclosed herein, R 5s Cycloalkyl groups can be C4 to C5. 20 C4 to C 15 Or C4 to C 10 Cycloalkyl. In any respect disclosed herein, substituted R 5s Cycloalkyl groups can be substituted C4 to C5. 20 C4 to or C4 to C 10 Cycloalkyl. In any respect disclosed herein, R 5s The aryl group can be C6 to C6. 20 C6 to C 15 Or C6 to C 10 Aryl. In any respect disclosed herein, the substituted R 5s The aryl group can be a substituted C6 to C6 group. 20 C6 to C 15 Or C6 to C10 Aryl. In any respect disclosed herein, R 5s Aryl alkyl groups can be C7 to C6. 20 C7 to C 15 Or C7 to C 10 Aryl alkyl groups. In any respect disclosed herein, substituted R 5s Aryl alkyl groups can be substituted C7 to C8. 20 C7 to C 15 Or C7 to C 10 Araneyl groups. Each substituent of a substituted alkyl group (generally or specifically), a substituted cycloalkyl group (generally or specifically), a substituted aryl group (generally or specifically), and / or a substituted araneyl group (generally or specifically) may be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, alkyl group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl groups (generally and specifically), and alkyloxy groups (generally and specifically) are disclosed independently herein. These halogen substituents, alkyl groups, and alkyloxy groups may be used without limitation for further description and may be used as R 5s Substituted groups (general and specific).

[0267] On the one hand, R 5s It can be 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, 3-pentyl, 2-methyl-1-butyl, tert-pentyl (2-methyl-2-butyl), 3-methyl-1-butyl, 3-methyl-2-butyl, or neopentyl (2,2-dimethyl-1-propyl); or alternatively, methyl, ethyl, isopropyl (2-propyl), tert-butyl (2-methyl-2-propyl), or neopentyl (2,2-dimethyl-1-propyl). In some aspects, R 5s Alkyl groups can be substituted. Substituted R 5s Each substituent of the alkyl group may independently be a halogen or an alkyloxy group; alternatively, a halogen; or alternatively, an alkyloxy group. Halogen substituents and alkyloxy substituents (general and specific) are described independently herein and these substituents may be used without limitation for further description as R 5s Substituted alkyl groups (general or specific).

[0268] On the one hand, R 5sIt can be cyclopentyl, substituted cyclopentyl, cyclohexyl, or substituted cyclohexyl; alternatively, cyclopentyl or substituted cyclopentyl; or alternatively, cyclohexyl or substituted cyclohexyl. In other respects, R 5s It can be a 2-substituted cyclohexyl, a 2,6-disubstituted cyclohexyl, a 2-substituted cyclopentyl, or a 2,5-disubstituted cyclopentyl; alternatively, a 2-substituted cyclohexyl or a 2,6-disubstituted cyclohexyl; alternatively, a 2-substituted cyclohexyl or a 2,6-disubstituted cyclohexyl; alternatively, a 2-substituted cyclopentyl or a 2,5-disubstituted cyclopentyl; alternatively, a 2-substituted cyclohexyl or a 2-substituted cyclopentyl; or alternatively, a 2,6-disubstituted cyclohexyl or a 2,5-disubstituted cyclopentyl. In one aspect, it is used as R 5s One or more substituents of a polysubstituted cycloalkyl group may be the same or different; alternatively, all substituents of a polysubstituted cycloalkyl group may be the same; or alternatively, all substituents of a polysubstituted cycloalkyl group may be different. Each substituent of a cycloalkyl group having a specified number of ring carbon atoms (generally or specifically) may independently be halogen, alkyl group, or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Halogen substituents, alkyl group substituents (generally and specifically), and alkyloxy group substituents (generally and specifically) are described independently herein and these substituents may be used without limitation for further description as R 5s Substituted cycloalkyl groups (general or specific).

[0269] In a non-restrictive aspect, R 5s It can be cyclohexyl, 2-alkylcyclohexyl, or 2,6-dialkylcyclohexyl; or alternatively, cyclopentyl, 2-alkylcyclopentyl, or 2,5-dialkylcyclopentyl. Alkyl substituents (general and specific) are described independently herein, and these alkyl substituents may be used without limitation for further description as R. 5s The alkylcyclohexyl (general or specific), dialkylcyclohexyl (general or specific), alkylcyclopentyl (general or specific), and / or dialkylcyclopentyl (general or specific). Typically, the alkyl substituents of the disubstituted cyclohexyl or cyclopentyl may be the same; or alternatively, the alkyl substituents may be different. In some non-limiting aspects, the heteroatom ligand structures and / or any heteroatom ligand chromium compound complex structures provided herein are R... 5s It can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, 2-tert-butylcyclohexyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-ditert-butylcyclohexyl. In other non-limiting respects, R 5sIt can be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, or 2-tert-butylcyclohexyl; or alternatively, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-diisopropylcyclohexyl, or 2,6-ditert-butylcyclohexyl. In one aspect, the heteroatom ligand structure provided herein and / or any heteroatom ligand chromium compound complex structure provided herein... 5s It can be cyclopentyl, 2-methylcyclopentyl, cyclohexyl or 2-methylcyclohexyl; alternatively, cyclopentyl or cyclohexyl; or alternatively, 2-methylcyclopentyl or 2-methylcyclohexyl.

[0270] On the one hand, R 5s It can be phenyl or substituted phenyl; alternatively, phenyl; or alternatively, substituted phenyl. In some respects, R 5s It can be a 2-substituted phenyl, a 4-substituted phenyl, a 2,4-disubstituted phenyl, a 2,6-disubstituted phenyl, or a 2,4,6-trisubstituted phenyl; alternatively, a 2-substituted phenyl or a 4-substituted phenyl; alternatively, a 2,4-disubstituted phenyl, a 2,6-disubstituted phenyl, or a 2,4,6-trisubstituted phenyl; alternatively, a 2,4-disubstituted phenyl or a 2,6-disubstituted phenyl; alternatively, a 2-substituted phenyl; alternatively, a 4-substituted phenyl; alternatively, a 2,4-disubstituted phenyl; alternatively, a 2,6-disubstituted phenyl; or alternatively, a 2,4,6-trisubstituted phenyl. In one aspect, used as R 5s One or more substituents of a polysubstituted phenyl group may be the same or different; alternatively, all substituents may be the same, or alternatively, all substituents may be different. Each substituent of the substituted phenyl group (general or specific) may independently be halogen, alkyl, or alkyloxy; alternatively, halogen or alkyl; alternatively, halogen or alkyloxy; alternatively, halogen; alternatively, alkyl; or alternatively, alkyloxy. Halogen substituents, alkyl substituents (general and specific), and alkyloxy substituents (general and specific) are described independently herein and these substituents may be used without limitation for further description as R 5s The substituted phenyl group (general or specific).

[0271] In a non-restrictive aspect, R 5s It can be phenyl, 2-alkylphenyl, 4-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, or 2,4,6-trialkylphenyl; alternatively, 2-alkylphenyl, 2,4-dialkylphenyl, 2,6-dialkylphenyl, or 2,4,6-trialkylphenyl. Alkyl substituents (general and specific) are described independently herein and these alkyl substituents may be used without limitation in further description as R5s Any alkyl-substituted phenyl group. Typically, the alkyl substituents of dialkylphenyl (general or specific) or trialkylphenyl (general or specific) can be the same; or alternatively, the alkyl substituents can be different. In some non-limiting aspects, R 5s It can be 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, 2,6-dimethylphenyl, or 2,4,6-trimethylphenyl.

[0272] Typically, having L 2s L of any heteroatom ligand and / or any heteroatom ligand chromium compound complex of the group 2s It can be a suborganogroup; alternatively, a suborganogroup composed of inert functional groups; alternatively, a alkylene group; or alternatively, an alkylene group. In one aspect, L... 2s The suborganogroup can be C1 to C2. 20 C1 to C 15 Or C1 to C 10 Suborganogroups. On one hand, L-shaped groups composed of inert functional groups. 2s Suborganogroups can be C1 to C1 composed of inert functional groups. 20 C1 to C 15 Or C1 to C 10 Suborganogroups. On the one hand, L 2s Alkylenes can be C1 to C2. 20 C1 to C 15 Or C1 to C 10 Alkylene.

[0273] On the one hand, it has L 2s L of any heteroatom ligand and / or any heteroatom ligand chromium compound complex of the group 2s It can be -(CR) P R P’ ) m -, where each R P and R P’ It can be independently hydrogen, methyl, ethyl, propyl, isopropyl, or butyl, and m can be an integer from 1 to 12. In some aspects, it has L 2s L of any heteroatom ligand and / or any heteroatom ligand chromium compound complex of the group 2sIt can be methylene (-CH2-), 1,2-vinyl (-CH2CH2-), 1,3-propenyl (-CH2CH2CH2-), 1,2-propenyl (-CH(CH3)CH2-), 2,2-propenyl (-C(CH3)2-), 1,4-butenyl (-CH2CH2CH2CH2-), or 2-methylpropyl-1,3-propenyl (-CH2CH(CH3)CH2-); or alternatively, methylene (-CH2-), 1,2-vinyl (-CH2CH2-), or 1,2-propenyl (-CH(CH3)CH2-).

[0274] On the one hand, it has L 2s L of any heteroatom ligand and / or any heteroatom ligand chromium compound complex of the group 2s It can be 1,2-cyclohexene, substituted 1,2-cyclohexene, 1,3-cyclohexene, substituted 1,3-cyclohexene, 1,4-cyclohexene, substituted 1,4-cyclohexene, 3,3'-bicyclohexene, substituted 3,3'-bicyclohexene, 4,4'-bicyclohexene, substituted 4,4'-bicyclohexene, bis(3-cyclohexene)methane, substituted bis(3-cyclohexene)methane, bis(4-cyclohexene)methane, substituted bis(4-cyclohexene)methane, 1,2-bis(3-cyclohexene)ethane, substituted... 1,2-bis(3-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. In some aspects, having L 2s L of any heteroatom ligand and / or any heteroatom ligand chromium compound complex of the group 2s It can be substituted 1,2-cyclohexylene, substituted 1,3-cyclohexylene, substituted 1,4-cyclohexylene, substituted 3,3'-bicyclohexylene, substituted 4,4'-bicyclohexylene, substituted bis(3-cyclohexylene)methane, substituted bis(4-cyclohexylene)methane, substituted 1,2-bis(3-cyclohexylene)ethane, substituted 1,2-bis(4-cyclohexylene)ethane, substituted 1,2-bis(3-cyclohexylene)propane, substituted 1,2-bis(4-cyclohexylene)propane, substituted 2,2-bis(3-cyclohexylene)propane, or substituted 2,2-bis(4-cyclohexylene)propane. In one aspect, it can be used as L... 2sEach substituent in the substituted cyclohexene, substituted bis(cyclohexene)methane, substituted bis(cyclohexene)ethane, or substituted 1,2-bis(3-cyclohexene)propane may be a hydrocarbon group. Substituents (general and specific) are disclosed independently herein and may be used without limitation in further description as L 2s Substituted cyclohexene (general or specific), substituted bis(cyclohexene)methane (general or specific), substituted bis(cyclohexene)ethane (general or specific), or substituted 1,2-bis(3-cyclohexene)propane (general or specific).

[0275] On the one hand, it has L 2s L of any heteroatom ligand and / or any heteroatom ligand chromium compound complex of the group 2s It can be 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)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. In some aspects, having L 2s L of any heteroatom ligand and / or any heteroatom ligand chromium compound complex of the group 2s It can be a substituted 1,2-phenylene, a substituted 1,3-phenylene, a substituted 1,4-phenylene, a substituted 3,3'-biphenylene, a substituted 4,4'-biphenylene, a substituted bis(3-phenylene)methane, a substituted bis(4-phenylene)methane, a substituted 1,2-bis(3-phenylene)ethane, a substituted 1,2-bis(4-phenylene)ethane, a substituted 1,2-bis(3-phenylene)propane, a substituted 1,2-bis(4-phenylene)propane, a substituted 2,2-bis(3-phenylene)propane, or a substituted 2,2-bis(4-phenylene)propane. In one aspect, it can be used as L... 2sEach substituent in the substituted phenylene (generally or specifically), substituted biphenylene (generally or specifically), substituted bis(phenylene)methane (generally or specifically), substituted bis(phenylene)ethane (generally or specifically), and / or substituted bis(phenylene)propane (generally or specifically) may be a hydrocarbon group. The hydrocarbon substituents (generally and specifically) are disclosed independently herein and may be used without limitation in further description and may be used as L 2s Substituted phenylene (general or specific), substituted biphenylene, substituted bis(phenylene)methane (general or specific), substituted bis(phenylene)ethane (general or specific) and / or substituted bis(phenylene)propane (general or specific).

[0276] Typically, having L 3s and / or L 4s L of any heteroatom ligand and / or any heteroatom ligand chromium compound complex of the group 3s and / or L 4s It can be an organic subgroup independently; alternatively, an organic subgroup composed of inert functional groups; alternatively, an alkyl subgroup; alternatively, an alkylene subgroup. In one aspect, L... 3s and / or L 4s The suborganogroup can be independently C1 to C2. 20 C1 to C 15 Or C1 to C 10 Suborganogroups. On one hand, L-shaped groups composed of inert functional groups. 3s and / or L 4s Suborganogroups can be independently composed of C1 to C1 inert functional groups. 20 C1 to C 15 Or C1 to C 10 Suborganogroups. On the one hand, L 3s and / or L 4s The alkylene group can be independently C1 to C2. 20 C1 to C 15 Or C1 to C 10 Hydroxyl group. On the one hand, L... 3s and / or L 4s Alkylenes can be independently C1 to C2. 20 C1 to C 15 Or C1 to C 10 Alkylene.

[0277] On the one hand, it has L 3s and / or L 4s L of any heteroatom ligand structure of the group and / or any heteroatom ligand chromium compound complex 3s and / or L 4s It can be -(CR) PR P’ ) m -, where each R P and R P’ It can be independently hydrogen, methyl, ethyl, propyl, isopropyl, or butyl, and m can be an integer from 1 to 12. In some aspects, it has L 3s and / or L 4s L of any heteroatom ligand structure of the group and / or any heteroatom ligand chromium compound complex 3s and / or L 4s It can be methylene (-CH2-), 1,2-vinyl (-CH2CH2-), 1,2-vinylene (-CH=CH-), 1,3-propenyl (-CH2CH2CH2-), 1,2-propenyl (-CH(CH3)CH2-), 2,2-propenyl (-C(CH3)2-), 1-methyl-1,2-vinylene (-C(CH3)=CH-), 1,4-butenyl (-CH2CH2CH2-) independently. CH2-), 1,3-butenyl (-CH2CH2CH(CH3)-), 2,3-butenyl (-CH(CH3)CH(CH3)-), 2-methylene-2,3-butenyl (-C(CH3)C(CH3)-), 3-methyl-1,3-butenyl (-CH2CH2C(CH3)2-), 1,2-cyclopentylene, 1,2-cyclohexylene, or 1,2-phenylene; alternatively, methylene (-CH2-), 1,2- Vinyl (-CH2CH2-), 1,3-propenyl (-CH2CH2CH2-), 1,2-propenyl (-CH(CH3)CH2-), 2,2-propenyl (-C(CH3)2-), 1,4-butenyl (-CH2CH2CH2-CH2-), 1,3-butenyl (-CH2CH2CH(CH3)-), 2,3-butenyl (-CH(CH3)CH(CH3)-), 1,2-cyclopentylene, 1,2-Cyclohexylene or 1,2-phenylene; or alternatively, 1,2-vinyl(-CH2CH2-), 1,3-propenyl(-CH2CH2CH2-), 1,2-propenyl(-CH(CH3)CH2-), 1,3-butenyl(-CH2CH2CH(CH3)-), 2,3-butenyl(-CH(CH3)CH(CH3)-), 1,2-cyclopentylene, 1,2-cyclohexylene or 1,2-phenylene.

[0278] The various aspects described herein relate to non-hydrogen substituents, such as halogen (or halogen group, halide), alkyl group, alkyloxy group, alkyl and / or alkoxy substituents. In one embodiment, each non-hydrogen substituent of any aspect of the claimed substituent can be halogen, alkyl group or alkyloxy group; alternatively, halogen or alkyl group; alternatively, halogen or alkyloxy group; alternatively, alkyl group or alkyloxy group; alternatively, halogen; alternatively, alkyl group; or alternatively, alkyloxy group. Each alkyl substituent can independently be C1 to C1. 10 Hydroxyl group; or alternatively, C1 to C5 alkyl group. Each alkyloxy substituent can independently be C1 to C5. 10 Hydroxyl group; or alternatively, C1 to C5 hydroxyl group. Each halide substituent may independently be a fluoride, chloride, bromide or iodide; alternatively, a fluoride or chloride; alternatively, a fluoride; alternatively, a chloride; alternatively, a bromide; or alternatively, an iodide.

[0279] In one aspect, any hydrocarbon substituent may independently be alkyl, aryl, or aralkyl; alternatively, alkyl; alternatively, aryl; or alternatively, aralkyl. In another aspect, any alkyl substituent 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 neopentyl; alternatively, methyl, ethyl, isopropyl, tert-butyl, or neopentyl; alternatively, methyl; alternatively, ethyl; alternatively, isopropyl; alternatively, tert-butyl; or alternatively, neopentyl. In one aspect, any aryl substituent may independently be phenyl, tolyl, xylyl, or 2,4,6-trimethylphenyl; alternatively, phenyl; alternatively, tolyl; alternatively, xylyl; or alternatively, 2,4,6-trimethylphenyl. In another aspect, any aralkyl substituent may independently be benzyl or ethylphenyl (2-phenylethyl-1-yl or 1-phenylethyl-1-yl); alternatively, benzyl; alternatively, ethylphenyl; alternatively, 2-phenylethyl-1-yl; or alternatively, 1-phenylethyl-1-yl.

[0280] In one aspect, any alkoxy substituent may independently be an alkoxy, aryloxy, or arylalkoxy; alternatively, an alkoxy; alternatively, an aryloxy or arylalkoxy. In another aspect, any alkoxy substituent may independently be a 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 neopentoxy; alternatively, a methoxy, ethoxy, isopropoxy, tert-butoxy, or neopentoxy; alternatively, a methoxy; alternatively, an ethoxy; alternatively, an isopropoxy; alternatively, a tert-butoxy; or alternatively, a neopentoxy. In one aspect, any aryloxy substituent may independently be phenoxy, tolyloxy, xyleneoxy, or 2,4,6-trimethylphenoxy; alternatively, phenoxy; alternatively, tolyloxy; alternatively, xyleneoxy; or alternatively, 2,4,6-trimethylphenoxy. In another aspect, any arylalkoxy substituent may independently be phenoxy.

[0281] Typically, heteroatom ligand transition metal compound complexes or transition metal compounds MX p The transition metal can be any transition metal atom. In one embodiment, the transition metal atom of the transition metal compound may include or be substantially composed of group 3-12, group 4-10, group 6-9, or group 7-8 transition metals. In some embodiments, the transition metal atom of the transition metal compound may include or be substantially composed of group 4 transition metals; alternatively, group 5 transition metals; alternatively, group 6 transition metals; alternatively, group 7 transition metals; alternatively, group 8 transition metals; alternatively, group 9 transition metals; or alternatively, group 10 transition metals. In one embodiment, the transition metal atoms of the transition metal compound may include or are substantially composed 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. Typically, heteroatom ligand transition metal compound complexes or transition metal compounds MX are used. pThe transition metal atom can have any positive oxidation state available to the transition metal atom. In one embodiment, the transition metal atom can have an oxidation state of +2 to +6; alternatively, +2 to +4; or alternatively, +2 to +3. In some embodiments, the transition metal compound MX p The transition metal atoms can have an oxidation state of +1; alternatively, +2; alternatively, +3; or alternatively, +4.

[0282] Typically, the chromium compounds or heteroatom ligand chromium compound complexes described herein may have the formula CrX. p Where X represents a monoanion ligand, and p(heteroatom ligands have the general formula [(HetLig)CrX] q L r ] 3-q (A) q) represents the number of monoanion ligands (and the oxidation state of chromium in the chromium compound). Monoanion ligands (X) and p are independent elements of the chromium compound or heteroatom ligand chromium compound complexes described herein and are described independently herein. The independent description of monoanion ligands (X) and p can be used in any combination without limitation for further description of the chromium compound or heteroatom ligand chromium compound complexes described herein.

[0283] Typically, chromium compounds (CrX) p Chromium atoms in chromium compounds (CrX) can have any positive oxidation state available to chromium atoms. In one aspect, chromium atoms can have oxidation states from +2 to +6; alternatively, from +2 to +4; or alternatively, from +2 to +3. In some aspects, chromium compounds (CrX) p Chromium atoms can have an oxidation state of +1; alternatively, +2; alternatively, +3; or alternatively, +4.

[0284] The monoanion (X) of a chromium compound can be any monoanion. In one aspect, the monoanion (X) can be a halide, carboxylate, β-diketonate, hydroxyl, nitrate, or chlorate. In some aspects, the monoanion (X) can be a halide, carboxylate, β-diketonate, or hydroxyl. In any aspect, the hydroxyl can be an alkoxy, aryloxy, or arylalkoxy. Typically, the hydroxyl (and its branches) is an anionic analog of the hydroxyl group. In other aspects, the monoanion (X) can be a halide, carboxylate, β-diketonate, or alkoxy; or alternatively, a halide or β-diketonate. In other aspects, the monoanion (X) can be a halide; alternatively, a carboxylate; alternatively, a β-diketonate; alternatively, a hydroxyl; alternatively, an alkoxy; or alternatively, an aryloxy. Typically, when the heteroatom ligand of a heteroatom-ligand chromium compound complex is a neutral heteroatom ligand, the number (p) of monoanions can be equal to the oxidation state of the chromium atom. When the heteroatom ligand of a heteroatom-ligand chromium compound complex is anionic heteroatom ligand, the number (p) of monoanions can be equal to one less than the oxidation state of the chromium atom. In one aspect, 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.

[0285] Typically, each halogen of a chromium compound can be independently fluorine, chlorine, bromine, or iodine; or alternatively, chlorine, bromine, or iodine. In one aspect, each halogen monoanion of a chromium compound can be chlorine; alternatively, bromine; or alternatively, iodine.

[0286] Typically, each carboxylate group in a chromium compound can be independently C1 to C2. 20 Carboxylate group; or alternatively, C1 to C 10Carboxylate ions. In one respect, each carboxylate ion in a chromium compound may independently be an acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate ion; or alternatively, valerate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, or dodecanoate ion. In some respects, each carboxylate group of the chromium compound may independently be an acetate, propionate, n-butyrate, valerate (n-valerate), neovalerate, hexanoate (n-hexanoate), n-heptanoate, octanoate (n-octanoate), 2-ethylhexanoate, n-nonanoate, decanoate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively, valerate (n-valerate), neovalerate, hexanoate (n-hexanoate), n-heptanoate, octanoate (n-octanoate), 2-ethylhexanoate, n-nonanoate, decanoate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively, hexanoate (n-hexanoate); alternatively, n-heptanoate; alternatively, octanoate (n-octanoate); or alternatively, 2-ethylhexanoate. In some respects, the carboxyl group of a chromium compound can be a trifluoromethanesulfonate group (trifluoroacetate group).

[0287] Typically, each β-diketone anion in a chromium compound can independently be any C1 to C2. 20 β-Diketone; or alternatively, any C1 to C 10 β-Diketone. In one respect, each β-diketone of the chromium compound may independently be acetylacetonate (i.e., 2,4-pentanedione), hexafluoroacetylacetonate (i.e., 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), or benzoylpyruvate; alternatively, acetylacetonate; alternatively, hexafluoroacetylacetonate; or alternatively, benzoylpyruvate.

[0288] Typically, each alkyl group in a chromium compound can be independently any C1 to C2 hydroxyl group. 20 Hydroxyl ions; or alternatively, any C1 to C 10 The alkyl ions. On one hand, each alkyl ion in a chromium compound can independently be C1 to C2. 20 Alkoxy group; alternatively, C1 to C 10 Alkoxy group; alternatively, C6 to C 20 Aromatic oxides; or alternatively, C6 to C 10 Aryloxy group. In one aspect, each alkoxy group in a chromium compound can independently be a methoxy, ethoxy, propoxy, or butoxy group; alternatively, a methoxy, ethoxy, isopropoxy, or tert-butoxy group; alternatively, a methoxy group; alternatively, an ethoxy group; alternatively, an isopropoxy group; or alternatively, a tert-butoxy group. In another aspect, the aryloxy group can be a phenoxy group.

[0289] In some non-limiting aspects, the chromium compound of the chromium compound and / or heteroatom ligand chromium compound complex may include, substantially consist of, or consist of: chromium halide (II), chromium carboxylate (II), or chromium β-diketonate (II); or alternatively, chromium halide (III), chromium carboxylate (III), or chromium β-diketonate (III). In other non-limiting aspects, the chromium compound of the chromium compound and / or heteroatom ligand chromium compound complex may include, substantially consist of, or consist of: chromium halide (II); alternatively, chromium halide (III); alternatively, chromium carboxylate (II); alternatively, chromium carboxylate (III); alternatively, chromium β-diketonate (II); or alternatively, chromium β-diketonate (III). Halogens, carboxylates, and β-diketones are independently described herein, and these halogens, carboxylates, and β-diketones, along with these independently described halogens, carboxylates, and β-diketones, can be used in any combination without limitation for further description of chromium compounds and / or heteroatom ligand chromium compound complexes. In other non-limiting aspects, chromium compounds and / or heteroatom ligand chromium compound complexes may include, may consist substantially of, or consist of: 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) trifluoromethanesulfonate, chromium(III) trifluoromethanesulfonate, chromium(II) nitrate, chromium(III) nitrate, chromium(II) acetylacetone, chromium(III) acetylacetone, chromium(II) hexafluoroacetylacetone, chromium(II) acetylacetone, chromium(III) hexafluoroacetylacetone. Chromium hexafluoroacetylacetonate (III), chromium benzoylpyruvate (II), or chromium benzoylpyruvate (III); alternatively, chromium chloride (III), chromium fluoride (III), chromium bromide (III), chromium iodide (III), chromium chloride (III) (THF) complex, chromium acetate (III), chromium 2-ethylhexanoate (III), chromium trifluoromethanesulfonate (III), chromium nitrate (III), chromium acetylacetonate (III), chromium hexafluoroacetylacetonate (III), or chromium benzoylpyruvate (III); alternatively, chromium chloride (III) or chromium acetylacetonate (III); alternatively, chromium chloride (III); or alternatively, chromium acetylacetonate (III).

[0290] In a non-limiting aspect, the one or more first-trained heteroatom ligand-metal compound complexes each comprising a first-trained heteroatom ligand may in particular be selected from any one or more heteroatom ligand chromium compound complexes having the following structures: i) structure NPFCrl, wherein R 1It is 2,6-dimethylphenyl, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,6-dimethylphenyl, R 3 For H, R 4 and R 5 R is phenyl, and X is chlorine; 1 It is 2,6-dimethylphenyl, R 3 For H, R 4 and R 5 It is 4-methoxyphenyl, and X is chlorine; R 1 It is 2,4,6-trimethylphenyl, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,4,6-trimethylphenyl, R 3 For H, R 4 and R 5 It is phenyl, and X is chlorine; and R 1 It is 2,4,6-trimethylphenyl, R 3 For H, R 4 and R 5 ii) The structure is 4-methoxyphenyl, and X is chlorine; 1 It is 2,6-dimethylphenyl, R 2 It is a phenyl group, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,4,6-trimethylphenyl, R 2 It is a phenyl group, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,6-dimethylphenyl, R 2 It is a phenyl group, R 3 For H, R 4 and R 5 R is phenyl, and X is chlorine; 1 It is 2,4,6-trimethylphenyl, R 2 It is a phenyl group, R 3 For H, R 4 and R 5 R is phenyl, and X is chlorine; 1 It is 2,6-dimethylphenyl, R 2 It is 4-methylbenzyl, R 3 For H, R 4 and R 5R is phenyl, and X is chlorine; 1 It is 2,6-dimethylphenyl, R 2 It is a phenyl group, R 3 For H, R 4 and R 5 It is 4-methoxyphenyl, and X is chlorine; R 1 It is 2,6-dimethylphenyl, R 2 It is 4-tert-butylphenyl, R 3 For H, R 4 and R 5 R is methyl, and X is chlorine; 1 It is 2,4,6-trimethylphenyl, R 2 It is 4-tert-butylphenyl, R 3 For H, R 4 and R 5 R is methyl, and X is chlorine; 1 It is 2,4,6-trimethylphenyl, R 2 It is 4-methylbenzyl, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,4,6-trimethylphenyl, R 2 It is 4-methylbenzyl, R 3 For H, R 4 and R 5 R is phenyl, and X is chlorine; 1 It is 3,5-dimethylphenyl, R 2 It is a phenyl group, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,4,6-trimethylphenyl, R 2 It is 4-methylbenzyl, R 3 For H, R 4 and R 5 It is 4-methoxyphenyl, and X is chlorine; R 1 It is 2,4,6-trimethylphenyl, R 2 It is 4-methylbenzyl, R 3 For H, R 4 For tert-butyl, R 5 R is phenyl, and X is chlorine; 1 It is 2,4,6-trimethylphenyl, R 2 It is 4-methylbenzyl, R 3 For H, R 4 For methyl, R 5 R is phenyl, and X is chlorine; 1 and R 2The linkage forms a 1,3-propenyl group, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 and R 2 The linkage forms a 1,4-butenyl group, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,4,6-trimethylphenyl, R 2 It is 4-methylbenzyl, R 3 For H, R 4 and R 5 The linkage forms a 1,4,-butenyl group, and X is chlorine; R 1 It is 2,4,6-trimethylphenyl, R 2 It is 4-methylbenzyl, R 3 For H, R 4 and R 5 The linkage forms a 2,2'-dimethylphenylene, and X is chlorine; iii) the structure GUCr1, wherein R 1 It is 2-methylphenyl, R 2a It is 2-methylphenyl, R 2b For H, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,6-dimethylphenyl, R 2a It is a phenyl group, R 2b For H, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine; R 1 It is 2,6-dimethylphenyl, R 2a It is a phenyl group, R 2b For H, R 3 For H, R 4 and R 5 R is phenyl, and X is chlorine; 1 It is 2,6-dimethylphenyl, R 2a and R 2b It is a phenyl group, R 3 For H, R 4 and R 5 iv) The structure is isopropyl, and X is chlorine; 12 It is 1,3-propenyl, L 23 It is 1,3-propenyl, R 4 and R 5 It is isopropyl, and X is chlorine; L 12It is 1,3-propenyl, L 23 It is 1,3-propenyl, R 4 and R 5 It is cyclopentyl, and X is chlorine; L 12 It is 1,3-propenyl, L 23 It is 1,3-propenyl, R 4 and R 5 It is cyclohexyl, and X is chlorine; L 12 It is 1,3-propenyl, L 23 It is 1,3-propenyl, R 4 and R 5 It is phenyl, and X is chlorine; L 12 It is 1,3-butenyl, L 23 It is 1,3-propenyl, R 4 and R 5 It is isopropyl, and X is chlorine; L 12 It is 1,3-butenyl, L 23 It is 1,3-propenyl, R 4 and R 5 It is cyclopentyl, and X is chlorine; L 12 It is 1,3-butenyl, L 23 It is 1,3-butenyl, R 4 and R 5 It is isopropyl, and X is chlorine; L 12 It is 1,3-butenyl, L 23 It is 1,3-butenyl, R 4 and R 5 It is phenyl, and X is chlorine; L 12 It is 1,2-vinylidene, L 23 It is 1,3-propenyl, R 4 and R 5 It is isopropyl, and X is chlorine; L 12 It is 1,2-vinylidene, L 23 It is 1,3-propenyl, R4 and R 5 It is cyclopentyl, and X is chlorine; L 12 It is 1,2-vinylidene, L 23 It is 1,3-propenyl, R 4 and R 5 It is cyclohexyl, and X is chlorine; L 12 It is 1,2-phenylene, L 23 For 1,2-vinyl, R 4 and R 5 It is isopropyl, and X is chlorine; and v) structure HCPACr2, where T is sulfur, L 12 For 1,2-vinylidene, R 3 For H, R 4 and R5 It is isopropyl, and X is chlorine; and T is sulfur, L 12 It is 1,2-phenylene, R 3 For H, R 4 and R 5 It is isopropyl, and X is chlorine.

[0291] In one non-limiting aspect, the one or more first-trained heteroatom ligands associated with the said one or more first-trained heteroatom ligand-metal compound complexes may be selected in particular from any one or more of HL 1, HL 2, HL 3, HL 4, HL 5, HL 6, HL 7, HL 8, and HL 9. In some non-limiting aspects, the one or more first-trained heteroatom ligand-metal compound complexes may be selected in particular from diphosphine chromium compound complexes, which may be chromium compound complexes of any one or more of HLCr 1, HLCr 2, HLCr 3, HLCr 4, HLCr 5, HLCr 6, HLCr 7, HLCr 8, and HLCr 9. In other non-limiting aspects, the one or more first training heteroatom ligand-metal compound complexes may be particularly selected from diphosphine chromium compound complexes, which may be one or more of chromium(III) chloride or chromium(III) acetylacetonate complexes selected from HLCr1, HLCr2, HLCr3, HLCr4, HLCr5, HLCr6, HLCr7, HLCr8 and HLCr9.

[0292]

[0293] Although not shown in all the names and formulas of chromium compounds and / or the formulas and structures of heteroatom ligand chromium compound complexes provided herein, those skilled in the art will recognize that the neutral ligand Q (heteroatom ligand general formula [(HetLig)CrX)) is a ligand of the general formula [(HetLig)CrX]. q L r ] 3-q (A) of L) can associate with chromium compounds and / or heteroatom ligand chromium compound complexes with neutral ligands that are not explicitly disclosed / described herein. Furthermore, it should be understood that while some of the chromium compounds and / or heteroatom ligand chromium compound complexes described / described / provided herein do not formally show the presence of neutral ligands, chromium compounds and / or heteroatom ligand chromium compound complexes having neutral ligands (e.g., nitriles and ethers, etc.) are implicitly and fully considered as potential chromium compounds and / or heteroatom ligand chromium compound complexes that can be used in catalyst systems in aspects of the invention described herein.

[0294] Typically, the neutral ligand of any chromium compound and / or heteroatom ligand chromium compound complex, when present, can independently be any neutral ligand that forms a separable compound with the chromium compound and / or heteroatom ligand chromium compound complex. In one respect, each neutral ligand can independently be a nitrile or an ether; alternatively, a nitrile; or alternatively, an ether. The number of neutral ligands q (of the general formula [(HetLig)CrX) q L r ] 3-q (A) r) can be any number of compounds that form separable compounds with chromium compounds and / or heteroatom ligand chromium compounds. In one respect, the number of neutral ligands can be 0 to 6; alternatively, 0 to 3; alternatively, 0; alternatively, 1; alternatively, 2; alternatively, 3; or alternatively, 4.

[0295] Typically, each nitrile ligand can be independently C2 to C3. 20 Nitriles; or alternatively, C2 to C 10 Nitriles. On the one hand, each nitrile ligand can independently be C2 to C3. 20 Aliphatic nitrile, C7 to C 20 Aromatic nitriles, C8 to C 20 Arane nitrile or any combination thereof; alternatively, C2 to C 20 Aliphatic nitriles; alternatively, C7 to C8 20 Aromatic nitrile; or alternatively, C8 to C90 nitrile. 20 Arane nitriles. In some respects, each nitrile ligand can independently be C2 to C3. 10 Aliphatic nitrile, C7 to C 10 Aromatic nitriles, C8 to C 10 Arane nitrile or any combination thereof; alternatively, C1 to C 10 Aliphatic nitriles; alternatively, C7 to C8 10 Aromatic nitrile; or alternatively, C8 to C90 nitrile. 10 Arane nitrile. In one respect, each aliphatic nitrile may independently be acetonitrile, propionitrile, butyronitrile, benzyl nitrile, or any combination thereof; alternatively, acetonitrile; alternatively, propionitrile; alternatively, butyronitrile; or alternatively, benzyl nitrile.

[0296] Typically, each ether ligand can be independently C2 to C3. 40 Ethers; alternatively, C2 to C 30 Ethers; or alternatively, C2 to C 20 Ethers. In one respect, each ether ligand can independently be C2 to C3. 40 Aliphatic ethers, C3 to C 40 Aliphatic cyclic ethers, C4 to C 40 Aromatic cyclic ethers; alternatively, C2 to C4 40 Aliphatic acyclic ethers or C3 to C4 ethers40 Aliphatic cyclic ethers; alternatively, C2 to C4 40 Aliphatic acyclic ethers; alternatively, C3 to C4. 40 Aliphatic cyclic ethers; or alternatively, C4 to C5 ethers. 40 Aromatic cyclic ethers. In some respects, each ether ligand can independently be C2 to C3. 30 Aliphatic ethers, C3 to C 30 Aliphatic cyclic ethers, C4 to C 30 Aromatic cyclic ethers; alternatively, C2 to C4 30 Aliphatic acyclic ethers or C3 to C4 ethers 30 Aliphatic cyclic ethers; alternatively, C2 to C4 30 Aliphatic acyclic ethers; alternatively, C3 to C4. 30 Aliphatic cyclic ethers; or alternatively, C4 to C5 ethers. 30 Aromatic cyclic ethers. In other respects, each ether ligand can independently be C2 to C3. 20 Aliphatic ethers, C3 to C 20 Aliphatic cyclic ethers, C4 to C 20 Aromatic cyclic ethers; alternatively, C2 to C4 20 Aliphatic acyclic ethers or C3 to C4 ethers 20 Aliphatic cyclic ethers; alternatively, C2 to C4 20 Aliphatic acyclic ethers; alternatively, C3 to C4. 20 Aliphatic cyclic ethers; or alternatively, C4 to C5 ethers. 20 Aromatic cyclic ethers. In some aspects, each ether ligand may independently be dimethyl ether, di-, 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, xylene 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; furan, benzofuran, isobenzofuran, dibenzofuran, or Any combination thereof; diphenyl ether, xylene 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, xylene ether.

[0297] Therefore, in any one of the one or more ground-state model structures and any one of the plurality of transition-state model structures, the model structure includes heteroatom ligands that can be independently selected from:

[0298]

[0299] in:

[0300] R 1 It can be hydrogen or C1 to C2. 20 Organic alkyl groups;

[0301] R 2 It can be C1 to C 20 Organic groups;

[0302] T can be oxygen or sulfur;

[0303] R 2a and R 2b It can be C1 to C independently. 20 Organic groups;

[0304] L 12 and L 23 It can be C2 to C independently. 20 Suborganogroup;

[0305] L 22 It can be C3 to C 20 Suborganogroup;

[0306] R 3 It can be hydrogen or C1 to C2. 20 Organic groups; and

[0307] R 4 and R 5 It can be hydrogen or C1 to C independently. 20 Organic groups;

[0308] Where R 1 and R 2 The L can be formed by any connection. 12r And L 12r It is C3 to C 30 Suborganogroup; and

[0309] Where R 4 and R 5 The L can be formed by any connection. 45 And L 45 It is C4 to C 30 Suborganogroup;

[0310] On the other hand, the model structure may include heteroatom ligands, which may be independently selected from NPF-1, NPA-1, Gu-1, Gu-2, Gu-3, Gu-4, Gu-5 or HCPA-1 as listed herein, wherein:

[0311] R 1 It can be hydrogen, C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon group;

[0312] R 2 It can be C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon group;

[0313] R 2a and R 2b Can be independently selected from C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon group;

[0314] L 12 and L 23 Can be independently selected from C2 to C 20 Hydroxyl or C2 to C 20 Heterohydrocarbon group;

[0315] L 22 It can be C3 to C 20 Hydroxyl or C3 to C 20 Heterohydrocarbon group;

[0316] R 3 It can be hydrogen, C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbons; and

[0317] R 4 and R 5 Can be independently selected from C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon group;

[0318] Where R 1 and R 2 The L can be formed by any connection. 12r And L 12r It can be C3 to C 20 Hydroxyl or C3 to C 20 Heterohydrocarbons; and

[0319] Where R 4 and R 5 The L can be formed by any connection. 45 And L 45 It can be C4 to C 20Hydroxyl or C4 to C 20 Heterohydrocarbon group.

[0320] For NPF-1, NPA-1, Gu-1, Gu-2, Gu-3, Gu-4, Gu-5, or HCPA-1 as listed in this document, use the R described independently in this document. 1 R 2 , T, R 2a R 2b R 3 R 4 R 5 L 12 L 22 L 23 Groups, and other aspects of the model structure that can be readily foreseen by those skilled in the art. The definition section that defines these terms is covered in these various choices for specific “R” and “L” portions (where “hydrocarbon,” “hydroene,” “heterocarbon,” or “heterocarbon” are mentioned) in NPF-1, NPA-1, Gu-1, Gu-2, Gu-3, Gu-4, Gu-5, or HCPA-1. For example, those covered in the name “hydrocarbon” or “hydroene” include, respectively: aryl and arylene; alkyl and alkyldiyl (or “alkylene”); cycloalkyl and cycloalkyldiyl (or “cycloalkylene”); aralkyl and aralkyldiyl (or “aralkylene”); and so on; wherein a specified number of carbon atoms is suitable for the selected group. Similarly, the definition section describes the portions that may be covered by the name “hydrocarbon” or “hydroene”.

[0321] In another aspect, in any one of the one or more ground-state model structures and any one of the plurality of transition-state model structures, the model structure comprises heteroatom ligands that can be independently selected from:

[0322]

[0323] in:

[0324] Each R 1s R 2s R 5s R 11s R 12s R 13s and R 14s It can be independently selected from hydrogen or C1 to C2. 20 Organic groups;

[0325] Each L 1s L 3s and L 4s Can be independently selected from C2 to C 20 Suborganogroup; and

[0326] Any two R 1s The L can be formed by any connection. 11s And L 11s It is C3 to C 30 Suborganogroup;

[0327] Any two R 2s The L can be formed by any connection. 22s And L 22s It is C3 to C 30 Suborganogroup;

[0328] Any R 11s and R 12s The L can be formed by any connection. 12s And L 12s It is C3 to C 30 Suborganogroup; and

[0329] Any R 13s and R 14s The L can be formed by any connection. 34s And L 34s It is C3 to C 30 Suborganogroups.

[0330] In another aspect, the model structure may include heteroatom ligands, 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 listed above, wherein:

[0331] Each R 1s R 2s R 5s R 11s R 12s R 13s and R 14s It can be independently selected from hydrogen, C1 to C2. 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon group;

[0332] Each L 1s L 3s and L 4s Can be independently selected from C2 to C 20 Hydroxyl or C2 to C 20 Heterohydrocarbon group;

[0333] Any two R 1s The L can be formed by any connection. 11s And L 11s It is C2 to C 20 Hydroxyl or C2 to C 20 Heterohydrocarbon group;

[0334] Any two R 2s The L can be formed by any connection. 22s And L 22s It is C2 to C 20 Hydroxyl or C2 to C 20 Heterohydrocarbon group;

[0335] Any R 11s and R 12s The L can be formed by any connection. 12s And L 12s It is C2 to C 20 Hydroxyl or C2 to C 20 Heterohydrocarbons; and

[0336] Any R 13s and R 14s The L can be formed by any connection. 34s And L 34s It is C2 to C 20 Hydroxyl or C2 to C 20 Heterohydrocarbon group.

[0337] For NRN-1, PRP-1, SRS-1, PNP-1, NRNRN-1, PRPRP-1, SRSRS-1, PRNRP-1 and / or NRPRN-1 as listed in this document, use the R described independently in this document. 1s R 2s R 5s R 11s R 12s R 13s R 14s L 1s L 3s L 4s L 11s L 12s L 22s and L 34s Groups, other aspects of the model structure can be readily foreseen by those skilled in the art. The definitional portions that follow define these terms in these various choices of "R" and "L" portions (where "hydrocarbon group," "hydroene group," "heterohydrocarbon group," or "heterohydrocarbon group") in NRN-1, PRP-1, SRS-1, PNP-1, NRNRN-1, PRPRP-1, SRSRS-1, PRNRP-1, or NRPRN-1.

[0338] Generally, the organoaluminum compound used in the catalyst systems disclosed herein can be any organoaluminum compound that, together with a heteroatom ligand chromium compound complex (or a chromium compound and a heteroatom ligand), can catalyze the formation of oligomer products. In one aspect, the organoaluminum compound can be an aluminum oxane, an alkylaluminum compound, or any combination thereof; alternatively, an aluminum oxane; or alternatively, an alkylaluminum compound. In another aspect, the alkylaluminum compound can be a trialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide, or any combination thereof. In some aspects, 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 aspects, the alkylaluminum compound can be a trialkylaluminum; alternatively, an alkylaluminum halide; or alternatively, an alkylaluminum alkoxide. In one aspect, the aluminum oxane used in the catalyst system utilized in the processes and systems can be any aluminum oxane that, together with a heteroatom ligand chromium compound complex (or a chromium compound and a heteroatom ligand), can catalyze the formation of oligomer products. In a non-limiting aspect, aluminum oxanes can have repeating units characterized by formula I:

[0339]

[0340] Wherein R' is a straight-chain or branched alkyl group. The alkyl groups of aluminum oxanes and alkylaluminum compounds are described independently herein and may be used without limitation to further describe aluminum oxanes and / or alkylaluminum compounds having formula I. Typically, n in formula I may be greater than 1; or alternatively, greater than 2. In one aspect, n may range from 2 to 15; or alternatively, from 3 to 10.

[0341] In one respect, each halide of any alkylaluminum halide disclosed herein may independently be a fluoride, chloride, bromide, or iodide; or alternatively, a chloride, bromide, or iodide. In one embodiment, each halide of any alkylaluminum halide disclosed herein may be a fluoride; alternatively, a chloride; alternatively, a bromide; or alternatively, an iodide.

[0342] On the one hand, each alkyl group in the aluminumoxane and / or alkylaluminum compound can independently be C1 to C2. 20 Alkyl; alternatively, C1 to C1 10Alkyl; or alternatively, C1 to C6 alkyl. In one aspect, each alkyl group of the aluminum oxane and / or alkylaluminum compound is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; alternatively, methyl, ethyl, butyl, hexyl, or octyl. In some aspects, each alkyl group of the aluminum oxane 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.

[0343] On the one hand, each alkoxy group of any alkylaluminum alkoxide disclosed herein can independently be C1 to C2. 20 Alkoxy, C1 to C 10 Alkoxy or C1 to C6 alkoxy groups. In one embodiment, each alkoxy group of any alkylaluminum alkoxide disclosed herein may independently be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy; alternatively, methoxy, ethoxy, butoxy, hexoxy, or octoxy. In some embodiments, each alkoxy group of any alkylaluminum alkoxide disclosed herein may independently be methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, n-hexoxy, or n-octoxy; alternatively, methoxy, ethoxy, n-butoxy, or isobutoxy; alternatively, methoxy; alternatively, ethoxy; alternatively, n-propoxy; alternatively, n-butoxy; alternatively, isobutoxy; alternatively, n-hexoxy; or alternatively, n-octoxy.

[0344] In one non-limiting aspect, useful trialkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, or mixtures thereof. In some non-limiting embodiments, useful trialkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, 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 may include trimethylaluminum; alternatively, triethylaluminum; alternatively, tripropylaluminum; alternatively, tri-n-butylaluminum; alternatively, triisobutylaluminum; alternatively, trihexylaluminum; or alternatively, tri-n-octylaluminum.

[0345] In one non-limiting embodiment, useful alkylaluminum halides may include diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In some non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In other non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride; alternatively, diethylaluminum bromide; alternatively, ethylaluminum dichloride; or alternatively, ethylaluminum sesquichloride.

[0346] In one non-limiting aspect, the aluminum oxane can be, includes, or substantially consists of: methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, tert-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or mixtures thereof. In some non-limiting aspects, the aluminum oxane can be, includes, or substantially consists of: methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, tert-butylaluminoxane, or mixtures thereof. In other non-limiting respects, the aluminum oxane can be, includes, or substantially consists of: methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane; alternatively, isopropylaluminoxane; alternatively, n-butylaluminoxane; alternatively, sec-butylaluminoxane; alternatively, isobutylaluminoxane; alternatively, tert-butylaluminoxane; alternatively, 1-pentylaluminoxane; alternatively, 2-pentylaluminoxane; alternatively, 3-pentylaluminoxane; alternatively, isopentylaluminoxane; or alternatively, neopentylaluminoxane.

[0347] Input variables of the model ground state structure and the model transition state structure

[0348] In one aspect, in the disclosed method, any one of the one or more training heteroatom ligand-metal compound complexes, and any one of the one or more target heteroatom ligand-metal compound complexes, may have independently selected from the following formulas:

[0349] [(HetLig)CrX q L r ] 3-q (A); where:

[0350] HetLig represents one or more of the first training heteroatom ligands;

[0351] X is an anionic ligand, and q is an integer;

[0352] L is a neutral ligand, and r is an integer.

[0353] Any two or more of the X and L ligands can be linked to form a polydentate ligand; and

[0354] The selected n input variables I 1 I 2 ...I n , corresponding to the one or more ground state model structures GS A1 ...GS Ap Any of the ground state model structures TS associated with one or more ground state model structures of equation (A) A1 TS A2 ...TS Am The structural or electronic properties of any one of them.

[0355] The input variables will differ depending on the type of heteroatom ligand and the specific heteroatom ligand coordinated with chromium in the ground-state and transition-state model structures of the training heteroatom ligand-metal compound complex. On one hand, when the model structure contains heteroatom ligands selected from the general formulas NPF-1, NPA-1, Gu-1, Gu-2, Gu-3, Gu-4, Gu-5, or HCPA-1 listed herein, the chromium heteroatom ligand portion can be independently selected from the following structures:

[0356]

[0357] Where 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 As defined herein, and where “*” in the structure indicates any additional bonding required from the following: [1] any of the one or more ground state model structures or any of the multiple transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes; [2] any of the one or more ground state model structures or any of the multiple transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes; or [3] any of the heteroatom ligand-metal compound complexes, the first training heteroatom ligand-metal compound complexes, and / or the first target heteroatom ligand-metal compound complexes.

[0358] On the one hand, and given the model structure containing chromium heteroatom ligand moieties 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 It may include or be selected from any one or more of the following variables:

[0359] (a) Cr-P distance

[0360] (b) Cr-N distance

[0361] (c) Cr-R distance on α-C

[0362] (d) P-Cr-N angle (degrees);

[0363] (e) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to or within the bonding distance of the Cr atom;

[0364] (f)Cr-NC angle (degrees);

[0365] (g) Distance outside the bag

[0366] (h)Cr---α-C distance

[0367] (i)Cr CHELPG (atomic charge);

[0368] (j)P CHELPG (atomic charge);

[0369] (k)N CHELPG (atomic charge);

[0370] (1) Cr-NCN dihedral angle (degrees);

[0371] (m)Cr-PNC dihedral angle (degrees);

[0372] (n)P-Cr-NC dihedral angle (degrees);

[0373] (o)PNCN dihedral angle (degrees);

[0374] (p) CCNC dihedral angle (degrees); or

[0375] (q) Percentage of buried volume.

[0376] Figure 1 , Figure 2A , Figure 2B and Figure 2C Some of the input variables described above are illustrated using the exemplary heteroatom ligand-chromium compound complex transition state. Referring to these figures, Cr-R is... Figure 1 The distance from Cr to the α-carbon of nitrogen in the structure, representing the distance from Cr to the group bonded to Cr. The Cr-α-C distance is... Figure 1 The direct distance from the α-carbon of nitrogen in the structure to which the R group is attached. (Reference) Figure 1 The C-Cr-N angle is formed by a carbon atom (i.e., a carbon atom grown from ethylene in the ground state and / or transition state) attached to a chromium atom on a substrate, a Cr atom, and a nitrogen atom of a heteroatom ligand complexed with a suitable ground-state and transition-state chromium atom. Those skilled in the art will be able to use... Figure 1 , Figure 2A , Figure 2B and Figure 2C To determine the corresponding n input variables I for the heteroatom ligand-chromium compound complex, the ground state of the heteroatom ligand-chromium compound complex, the transition state of the heteroatom ligand-chromium compound complex, and the chromium heteroatom ligand portions NPFCrM-1, NPACrM-1, GuCrM-1, GuCrM-2, GuCrM-3, GuCrM-4, GuCrM-5, or HCPACrM-1 described in this paper. 1 I 2 ...I n .

[0377] Figure 2A-2C Further explanations and definitions are provided for some of these input variables. For example, these graphs illustrate descriptors that can be extracted for machine learning analysis, including: Figure 2A , geometric descriptor and description of the electrostatic charge input variable; Figure 2B The definition of the percentage of buried volume; and Figure 2CThe definition of the outer bag distance. As shown in the figure, the outer bag distance is defined as follows: outer bag distance (d) = R(Cr-N1)·sin(∠Cr-N1-P). That is, the outer bag distance is the Cr-N1 distance multiplied by the sine of the Cr-N1-P angle, which describes how far the Cr metal is from the (P, N) ligand. The burial volume percentage is defined as the degree to which the first coordination sphere at the center of the Cr metal is occupied by the (P, N) ligand, 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

[0378] In another aspect, when the model structure includes a heteroatom ligand selected from the general formulas NRN-1, PRP-1, SRS-1, PNP-1, NRNRN-1, PRPRP-1, SRSRS-1, PRNRP-1, or NRPRN-1 as listed herein, the chromium heteroatom ligand moiety can be independently selected from the following structures:

[0379]

[0380] Where R 1s R 2s R 5s R 11s R 12s R 13s R 14s L 1s L 3s L 4s L 11s L 22s L 12sr and L 34sAs defined herein, and where “*” in the structure indicates any additional bonding required from the following: [1] any of the one or more ground state model structures or any of the multiple transition state model structures derived from the one or more first training heteroatom ligand-metal compound complexes; [2] any of the one or more ground state model structures or any of the multiple transition state model structures derived from the one or more first target heteroatom ligand-metal compound complexes; or [3] any of the heteroatom ligand-metal compound complexes, the first training heteroatom ligand-metal compound complexes, and / or the first target heteroatom ligand-metal compound complexes.

[0381] On the one hand, and given the model structure containing chromium heteroatom ligand moieties NRNCrM-1, PRPCrM-1, SRSCrM-1, PNPCrM-1, NNRNCrM-1, PPRPCrM-1, SRRRSCrM-1, PRNRPCrM-1, or NRPRNCrM-1, n input variables I 1 I 2 ...I n It may include or be selected from any one or more of the following variables:

[0382] (a) First, second or third Cr-N distance

[0383] (b) First, second or third Cr-P distance

[0384] (c) First or second Cr-S distance

[0385] (d) Any one or more N-Cr-N angles (degrees);

[0386] (e) Any one or more P-Cr-P angles (degrees);

[0387] (f) Any one or more S-Cr-S angles (degrees);

[0388] (g) Any one or more S-Cr-N angles (degrees);

[0389] (h) Any one or more N-Cr-P angles (degrees);

[0390] (i) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to or within the bonding distance of the Cr atom;

[0391] (j) C-Cr-P angle (degrees);

[0392] (k)C-Cr-S angle (degrees);

[0393] (1) Cr-NC angle (degrees);

[0394] (m)Cr-PC angle (degrees);

[0395] (n)Cr-SC angle (degrees);

[0396] (o)Cr-PC angle (degrees);

[0397] (p)Cr-R distance on α-C

[0398] (q) Distance outside the bag

[0399] (r)Cr---α-C;

[0400] (s)Cr CHELPG (atomic charge);

[0401] (t) Any P CHELPG (atomic charge);

[0402] (u) Any N CHELPG (atomic charge);

[0403] (v) Any chelated Cr-NCC dihedral angle (degrees);

[0404] (w) Any chelated Cr-PCC dihedral angle (degrees);

[0405] (x) Any chelated Cr-SCC dihedral angle (degrees); or

[0406] (y) Percentage of buried volume.

[0407] Figure 2B The definition of the percentage of buried volume is explained, and Figure 2C This explains the definition of the distance outside the bag.

[0408] Performance parameters and adjusting input variables to approximate the corresponding output variables

[0409] In the method disclosed herein, based on the one or more n input variables I identified from the machine learning model 1 I 2 ...I n This generates a first target heteroatom ligand-metal compound complex for olefin oligomerization. The first target heteroatom ligand-metal compound complex is characterized by n output variables O. 1 O 2 ...O n Each output variable has a corresponding ground state model structure GS. B1 ...GSBx (x is an integer) or multiple transition state model structures TS associated with one or more ground state model structures. B1 TS B2 ...TS By A quantitative value of any one of the structural or electronic properties of (y is an integer). The first target heteroatom ligand-metal compound complex contains a first target heteroatom ligand, which has been generated by evaluating a first training model against a machine learning model to discover the expected adjustment that will generate the first target heteroatom ligand.

[0410] On one hand, one or more performance parameters related to olefin oligomerization are identified, and the values ​​of these performance parameters for the one or more first training heteroatom ligand-metal compound complexes and the first target heteroatom ligand-metal compound complex are calculated and evaluated, with experimental verification and further testing and redesign performed against training compounds. In this way, catalyst performance can be predicted and improved.

[0411] As disclosed herein, for 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 Each of the multiple transition state model structures TS A1 TS A2 ...TS Am Each of the n input variables I is assigned to each of the n input variables. 1 I 2 ...I n The quantitative values ​​can be assigned based on calculated values, measured values, or estimated values, or any combination thereof. Furthermore, for the one or more ground-state model structures GS... A1 ...GS Ap Each of the multiple transition state model structures TS A1 TS A2 ...TS Am Each of the n input variables I is assigned to each of the n input variables. 1 I 2 ...I n The quantitative value can be either the original value or the normalized value. Additionally, the ground-state model structure GS is determined. A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS AmThe relative energy of each of the n input variables I, these determined relative energies can independently be the relative energy of the possible conformational ensembles of the ground state model structure and the transition state model structure, or the relative energy of a specific conformation. Similarly, the n input variables I... 1 I 2 ...I n One or more input variables associated with [1] ΔG(TS-GS) or ΔΔG(TS-GS) or [2] ΔG(TS-TS) or ΔΔG(TS-TS), these ΔG or ΔΔG energy differences may be based on Boltzmann ensemble ΔG or ΔΔG values. For example, as explained in detail in this disclosure, in one aspect, density functional theory (DFT) calculations can be used to calculate the ground-state model structure GS derived from the one or more first training heteroatom ligand-metal compound complexes. A1 ...GS Ap Any one or more of the transition state model structures TS A1 TS A2 ...TS Am Any one of them. Furthermore, the machine learning model used to generate the disclosed method may include a Gaussian process algorithm or a random forest algorithm.

[0412] According to one aspect of this disclosure, the one or more performance parameters associated with the 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 herein as selectivity or product selectivity); (c) heteroatom ligand-metal compound complex productivity (also referred herein as activity / productivity or oligomer productivity); or (d) any combination thereof. More specifically, in one aspect, the one or more performance parameters associated with the 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 plus 1-octene; (g) trimerization selectivity for 1-hexene; (h) tetramerization selectivity for 1-octene; (i) 1-octene efficiency of the fourth ethylene addition; or any combination thereof. Based on these performance parameters, the relevant ground state model structure and the relevant transition state model structure can include the following or can be selected as follows.

[0413] Regarding olefin productivity, the performance parameter associated with the olefin oligomerization reaction may be the productivity of the heteroatom ligand-metal compound complex 1-hexene, the productivity of 1-octene, or the total productivity of 1-hexene and 1-octene. Therefore, when the performance parameter is one of these productivity parameters: [1] the one or more ground-state model structures GS derived from one or more first training heteroatom ligand-metal compound complexes. A1 ...GSAp It may include the following or may be selected independently from the following: GS I -I, GS I -II, GS I -III, GS I -IV, GS I -V、GS I -VI, GS I -VII, or any combination thereof; [2] the multiple transition state model structures TS derived from one or more first-trained heteroatom ligand-metal compound complexes. A1 TS A2 ...TS Am It may include the following or may be selected independently from the following: TS I -I、TS I -II、TS I -III, TS I -IV、TS I -V or any combination thereof; [3] one or more ground-state model structures GS derived from the first target heteroatom ligand-metal compound complex. B1 ...GS Bp It may include the following or may be selected independently from the following: GS T -I, GS T -II, GS T -III, GS T -IV, GS T -V、GS T -VI, GS T -VII or any combination thereof; [4] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm It may include the following or may be selected independently from the following: TS T -I、TS T -II、TS T -III, TS T -IV、TS T -V or any combination thereof. When the one or more performance parameters associated with olefin oligomerization include or are selected from heteroatom ligand-metal compound complex productivity, it can be determined based on the number of grams of olefin oligomers per hour per gram of heteroatom ligand-metal compound complex (grams of 1-hexene, grams of 1-octene, or the total number of grams of 1-hexene and 1-octene).

[0414] On the one hand, for example, Figure 3A reaction scheme for calculating / determining / estimating the 1-hexene switching frequency is described, illustrating various ground and transition states, and illustrating the transition state energy barriers that contribute to the 1-hexene switching frequency. The 1-hexene switching frequency is then converted to the 1-hexene productivity. In another aspect, [the following can be used]... Figure 3 The ground state and transition state plus Figure 4 The ground and transition states described in the diagram are used to calculate / determine / estimate the 1-octene transition frequency. Figure 4 This describes the 1-octene frequency conversion reaction scheme, where the ground state and transition state must be consistent with... Figure 3 The ground state and transition state, starting from GS-VI, are included together. Therefore, Figure 3 Plus Figure 4 All transition state energy barriers that contribute to the 1-octene switching frequency are explained, and the 1-octene switching frequency can then be converted into 1-octene productivity.

[0415] When the conversion frequency of 1-hexene plus the conversion frequency of 1-octene (and thus the combined conversion frequency) is determined, the 1-hexene conversion frequency and the 1-octene conversion frequency can be determined separately using the procedure illustrated herein for determining the 1-hexene conversion frequency. The separately determined conversion frequencies are then added together to obtain the combined conversion frequency (the total conversion frequency of 1-hexene plus 1-octene). The combined conversion frequency can then be converted into the productivity of 1-hexene plus 1-octene.

[0416] Regarding olefin selectivity, when the performance parameter related to olefin oligomerization is product selectivity (which can be simply referred to as the C6 / C8 ratio or C8 / C6 ratio), Figure 5A The pathways for the formation of 1-hexene and 1-octene are described. The ground state and transition state names correspond to the ground state and transition state structures disclosed herein. As shown in the figure, the formation of both 1-hexene and 1-octene can proceed via a common ground state GS-VI. The olefin selectivity is then determined by whether 1-hexene is formed via β-hydride elimination and reductive elimination through TS-III, or by ethylene insertion into GS-VI to provide ground state GS-V and then via TS-IV to form cyclononane GS-VII, which itself then undergoes β-hydride elimination and reductive elimination to form 1-octene. The product selectivity can then be determined using the rate-determining transition states (typically TS-III and TS-IV) by comparing the relative amounts of ground state GS-VI undergoing β-hydride elimination to 1-hexene with those of ground state GS-VI undergoing ethylene insertion to form cyclononane GS-VII.

[0417] Therefore, regarding selectivity, when the performance parameter associated with the olefin oligomerization reaction is 1-hexene selectivity or 1-octene selectivity (which can be simply referred to as the C6 / C8 ratio): [1] the one or more ground-state model structures GS derived from one or more first-trained heteroatom ligand-metal compound complexes. A1 ...GS Ap May include GS I -VI; [2] the multiple transition state model structures TS derived from one or more first-trained heteroatom ligand-metal compound complexes. A1 TS A2 ...TS Am It can include TS I -III and TS I -IV; [3] one or more ground-state model structures GS derived from the first target heteroatom ligand-metal compound complex. B1 ...GS Bp This can include GS T -VI; and / or [4] the multiple transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm It can include TS T -III and TS T -IV. Therefore, when the 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 generated by the common ground state (typically GS-VI) and 1) the transition state leading to the production of 1-hexene (typically TS-III) and 2) the transition state leading to the production of 1-octene (typically TS-IV). The amounts of 1-hexene and 1-octene can then be determined using the calculated Gibbs free energy difference ΔΔG[TS(1-hexene)-TS(1-octene)] compared to a graph of the natural logarithms of a set of heteroatom ligand-metal compound complexes, for which the experimentally determined Gibbs free energy difference and the experimentally determined masses of 1-hexene and 1-octene are known. Alternatively, the experimentally determined masses of 1-hexene and 1-octene can be replaced by the calculated activity / productivity calculated / determined / estimated by the methods described herein (via determining the transition frequencies of 1-hexene and 1-octene production).

[0418] The selective oligomerization of ethylene into 1-hexene and 1-octene can produce byproducts. Therefore, the selectivity of the trimerization catalytic cycle for 1-hexene (also known as the trimerization cycle selectivity for 1-hexene) and / or the selectivity of the tetramerization catalytic cycle for 1-octene (also known as the tetramerization cycle selectivity for 1-octene) can be performance parameters related to olefin oligomerization influenced by heteroatom ligand-metal compound complexes. The trimerization cycle selectivity for 1-hexene is the number of moles of 1-hexene produced divided by the number of moles of 1-hexene produced, plus the number of moles of non-1-hexene byproducts produced through the trimerization catalytic cycle. The tetramerization cycle selectivity for 1-octene is the number of moles of 1-octene produced divided by the number of moles of 1-octene produced, plus the number of moles of non-1-octene byproducts produced through the tetramerization catalytic cycle.

[0419] The trimerization cycle selectivity for 1-hexene and the tetramerization cycle selectivity for 1-octene can also be used to focus on specific non-1-hexene byproducts produced by the trimerization catalytic cycle and / or specific non-1-octene byproducts produced by the tetramerization catalytic cycle. In these cases, the trimerization cycle selectivity will be the number of moles of 1-hexene produced divided by the number of moles of 1-hexene produced plus the number of moles of specific non-1-hexene byproducts produced in the trimerization catalytic cycle, while the tetramerization cycle selectivity for 1-octene will be the ratio of the number of moles of 1-octene produced to the total number of moles of 1-octene produced plus the number of moles of specific non-1-octene byproducts produced in the tetramerization catalytic cycle.

[0420] When 1-hexene or 1-octene produced in trimerization and / or tetramerization replaces one of the ethylene components in the trimerization and / or tetramerization catalytic cycles, a specific set of non-1-hexene byproducts produced via the trimerization catalytic cycle and / or non-1-octene byproducts produced via the tetramerization catalytic cycle can occur. Particularly relevant is the formation of complexes between the resulting 1-hexene or 1-octene and chromium compounds resembling... Figure 5A The ground-state structures of GS-II in trimerization and tetramerization catalytic cycles are depicted. 1-Hexene or 1-octene participating in the trimerization and / or tetramerization cycles can exhibit two different orientations, producing two structurally different chromocyclopentanes. Figure 5B and Figure 5C This demonstrates how 1-hexene or 1-octene can be propagated via trimerization and / or tetramerization catalytic cycles to produce branched decene, branched dodecene, and / or branched tetradecene.

[0421] Furthermore, each different 1-hexene or 1-octene orientation that produces two structurally different substituted cyclopentanes produces two different branched decenes (for 1-hexene insertion) and two different branched dodecenes (for 1-octene insertion) in a trimerization catalytic cycle and / or two different branched dodecenes (for 1-hexene insertion) and two different branched tetradecenes (for 1-octene insertion) in a tetramerization catalytic cycle.

[0422] The methods disclosed herein can be used to design / identify heteroatom ligand-metal compound complexes for olefin oligomerization that exhibit desired trimerization cycle selectivity for 1-hexene (based on all non-1-hexene catalytic trimerization byproducts or based on specific non-1-hexene catalytic trimerization byproducts) and / or desired tetramerization cycle selectivity for 1-octene (based on all non-1-octene hexene catalytic trimerization byproducts or based on specific non-1-hexene catalytic trimerization byproducts).

[0423] The trimerization cycle selectivity for 1-hexene (based on all non-1-hexene-catalyzed trimerization byproducts or based on specific / specific non-1-hexene-catalyzed trimerization byproducts) can be determined using the different methods described herein.

[0424] In a non-limiting first method, the amounts of 1-hexene and non-1-hexene catalytic trimerization byproducts can be determined by the ratio of non-1-hexene catalytic trimerization byproducts to 1-hexene. In this method, the ratio of non-1-hexene catalytic trimerization byproducts to 1-hexene for each non-1-hexene catalytic trimerization byproduct is determined by determining the Gibbs free energy difference ΔΔG between 1) the rate-determining transition state / reaction step leading to 1-hexene production and 2) the rate-determining transition state / reaction step leading to the non-1-hexene catalytic trimerization byproduct, and the trimerization cycle selectivity for 1-hexene is based on this ratio. The amounts of 1-hexene and non-1-hexene catalytic trimerization byproducts can then be determined by comparing the calculated Gibbs free energy difference ΔG[TS(1-hexene) - TS(non-1-hexene catalytic trimerization byproducts)] with the natural logarithm of a set of heteroatom ligand-metal compound complexes. For these complexes, the experimentally determined Gibbs free energy difference and the experimentally determined amounts of 1-hexene and non-1-hexene catalytic trimerization byproducts are known. It should be noted that the selectivity-determining transition state / reaction step of the trimerization catalytic cycle is not predetermined and can only be determined by performing necessary calculations on the trimerization catalytic cycle; the specific selectivity-determining transition state / reaction step can be ligand-dependent.

[0425] As an example, the trimerization cycle selectivity of p-1-hexene based on branched decene and / or dodecene can be used... 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 The calculations are performed using the proposed trimerization pathway described in GS-IIb / GS-IIIb / GS-IVb / GV-VIb / TS-IIIb branched decene or dodecene pathways. In this example, 1) will be calculated. Figure 5A The Gibbs free energy of the transition state / reaction step that determines the rate of production of 1-hexene, as described in [2] Figure 5B The Gibbs free energy of the rate-determining step / reaction step for each branched decene and / or branched dodecene produced in the trimerization cycle described in the figure, and 3) Figure 5C The Gibbs free energy of the rate-determining step / reaction step produced in each branched decene and / or branched dodecene in the trimerization cycle described in the figure is then used to calculate the Gibbs free energy difference for each branched decene and / or dodecene used in the calculation of the trimerization cycle selectivity for 1-hexene, ΔG[TS(1-hexene)-TS(non-1-hexene catalyzed trimerization byproducts)].

[0426] Then, for each branched decene and / or dodecene used in the calculation of the trimerization cycle selectivity of 1-hexene, a mathematical relationship is 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 which the ratio of 1-hexene to branched decene or dodecene has been experimentally determined. This mathematical relationship can then be used to determine, via interpolation and extrapolation, the amounts of 1-hexene and each branched decene and / or dodecene used in the calculation of the trimerization cycle selectivity of 1-hexene, where the experimental amounts of 1-hexene and each branched decene and / or dodecene are unknown, for the calculated Gibbs free energy difference ΔΔG[TS(1-hexene)-TS(branched decene or branched dodecene)].

[0427] A second, non-limiting method for determining the trimerization cycle selectivity for 1-hexene (based on all non-1-hexene catalytic trimerization byproducts or based on a specific / specific non-1-hexene catalytic trimerization byproduct) replaces the molar number of 1-hexene and the molar number of each non-1-hexene catalytic trimerization byproduct with their respective calculated activities / productivity determined by switching frequencies for the 1-hexene and each non-1-hexene catalytic trimerization byproduct utilized in the calculation of the trimerization cycle selectivity for 1-hexene. For example, if the trimerization cycle selectivity for 1-hexene is determined based on the number of moles of 1-hexene and the number of moles of branched decene and / or branched dodecene produced when 1-hexene and / or 1-octene participate in the trimerization catalytic cycle, then the number of moles of 1-hexene produced in 1) can be replaced with the calculated activity / productivity determined by using the switching frequencies of all ground and transition states in the GS-II / GS-III / GS-IV / GS-VI / TS-III pathway, and the number of moles of each branched decene and / or branched dodecene produced in 2) can be replaced with the appropriate calculated activity / productivity determined by switching frequencies for each branched decene and / or branched dodecene produced by using the GS-IIa / GS-IIIa / GS-IVa / GS-VIa / TS-IIIa pathway and j or GS-IIb / GS-IIIb / GS-IVb / GS-VIb / TS-IIIb pathway. If other non-1-hexene-catalyzed trimerization byproducts are included in determining the trimerization cycle selectivity for 1-hexene, the molar number of these other non-1-hexene-catalyzed trimerization byproducts will be replaced by the calculated activity / productivity determined using all ground and transition states in the pathway suitable for non-1-hexene-catalyzed trimerization byproducts, calculated using the switching frequency.

[0428] The tetramerization cycle selectivity of 1-octene (based on all non-1-octene catalytic tetramerization byproducts or based on specific / specific non-1-octene catalytic trimerization byproducts) can be determined using the different methods described herein.

[0429] In a non-limiting first method, the amounts of 1-octene and non-1-octene catalytic tetramerization byproducts can be determined by the ratio of the non-1-octene catalytic tetramerization byproduct to 1-octene. In this method, the ratio of the non-1-octene catalytic tetramerization byproduct to 1-hexene for each non-1-octene catalytic tetramerization byproduct is determined by determining the Gibbs free energy difference ΔΔG between 1) the rate-determining transition state / reaction step leading to the production of 1-octene and 2) the rate-determining transition state / reaction step leading to the non-1-octene catalytic tetramerization byproduct, and the tetramerization cycle selectivity for 1-octene is based on this ratio. The amounts of 1-octene and non-1-octene catalytic trimerization byproducts can then be determined by comparing the calculated Gibbs free energy difference ΔG[TS(1-octene) - TS(non-1-octene catalytic tetramerization byproduct)] with the natural logarithm of a set of heteroatom ligand-metal compound complexes. For the complexes, the experimentally determined Gibbs free energy difference and the experimentally determined amounts of 1-octene and non-1-octene catalytic trimerization byproducts are known. It should be noted that the selectivity-determining transition state / reaction step of the tetramerization catalytic cycle is not predetermined and can only be determined by performing necessary calculations on the tetramerization catalytic cycle: the specific selectivity-determining transition state / reaction step can be ligand-dependent.

[0430] As an example, the tetramerization cycle selectivity of 1-octene based on branched dodecene and / or tetradecene can be used Figure 5A (via the GS-II / GS-III / GS-IV / GS-VI / GS-V / TS-IV / GS-VII / TS-V octene pathway) Figure 5B (via the GS-IIa / GS-IIIa / GS-IVa / GS-VIa / GS-Va / TS-IVa / GS-VIIa / TS-Va branched dodecene or tetradecene pathway) and Figure 5C The calculation is performed using the proposed tetramerization pathway described in GS-IIb / GS-IIIb / GS-IVb / GS-VIb / GS-Vb / TS-IVb / GS-VIIb / TS-Vb branched dodecene or tetradecene pathways. In this example, 1) will be calculated. Figure 5A The Gibbs free energy of the transition state / reaction step that determines the rate of 1-octene, as described in [2] Figure 5B The Gibbs free energy of the rate-determining step / reaction step for each branched dodecene and / or branched tetradecene produced in the tetramerization cycle described in the figure, and 3) Figure 5CThe Gibbs free energy of the rate-determining step / reaction step produced in each branched dodecene and / or branched tetradecene in the trimerization cycle described is then used to calculate the Gibbs free energy difference, ΔΔG[TS(1-octene) - TS(non-1-octene catalyzed trimerization byproduct)], for each branched dodecene and / or tetradecene used in the calculation of trimerization cycle selectivity for 1-hexene. Then, for each branched dodecene and / or tetradecene used in the calculation of tetradecene cycle selectivity for 1-octene, the mathematical relationship 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 which the ratio of 1-octene to branched dodecene or tetradecene was experimentally determined. Then, using this mathematical relationship, the amount of 1-octene and each branched dodecene and / or tetradecene used in the calculation of the tetramerization cycle selectivity of 1-octene is determined by interpolation and extrapolation for 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 unknown.

[0431] A second, non-limiting method for determining the tetramerization cycle selectivity for 1-octene (based on all non-1-octene catalytic tetramerization byproducts or based on a specific non-1-octene catalytic tetramerization byproduct) replaces the molar number of 1-octene and the molar number of each non-1-octene catalytic tetramerization byproduct with their respective calculated activities / productivity determined using transition frequencies for the 1-octene and each non-1-octene catalytic tetramerization byproduct utilized in the calculation of the tetramerization cycle selectivity for 1-octene. For example, if the tetramerization cycle selectivity for 1-octene is determined based on the molar number of 1-octene produced when 1-hexene and / or 1-octene participate in the tetramerization catalytic cycle and the molar number of branched dodecene and / or branched tetradecene produced, then the molar number of 1-octene produced in 1) can be replaced with the calculated activities / productivity determined using the transition frequencies of all ground and transition states in the GS-II / GS-III / GS-IV / GS-VI / GS-V / TS-IV / GS-VII / TS-V pathways, and... Replace the molar number of each branched dodecene and / or branched tetradecene produced in 2) with the appropriate calculated activity / productivity determined by calculations using the transition frequencies of all ground and transition states in the GS-IIa / GS-IIIa / GS-IVa / GS-VIa / GS-Va / TS-IVa / GS-VIIa / TS-Va pathway and / or the GS-IIb / GS-IIIb / GS-IVb / GS-VIb / GS-Vb / TS-IVb / GS-VIIb / TS-Vb pathway. If other non-1-octene catalytic tetramerization byproducts are included in determining the tetramerization cycle selectivity for 1-octene, the molar number of these other non-1-octene catalytic tetramerization byproducts will be replaced with the calculated activity / productivity determined by calculations using the transition frequencies of all ground and transition states in the pathway suitable for non-1-octene catalytic tetramerization byproducts.

[0432] Regarding olefin purity, when the performance parameter related to olefin oligomerization is 1-hexene purity... Figure 6 The pathways through which 1-hexene can be formed and the pathways through which six-carbon impurities can appear in the formation of 1-hexene are explained. The ground state and transition state names correspond to those ground state and transition state structures disclosed herein. Referring to the figure, 1-hexene (C6) can appear, 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 another aspect, in Figure 6In this process, 1-hexene (C6) impurities can appear, for example, through 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.

[0433] In this respect, Figure 6 This demonstrates that various sets of ground and transition states can control the selectivity for producing 1-hexene versus six-carbon impurities or (1-hexene impurities). This concept is... Figure 7 The text explains that the energy difference of the transition state (TS) controls the pathway for the production of 1-hexene and the pathway for the production of C6 impurities (1-hexene impurities).

[0434] Therefore, regarding olefin purity, specifically "1-hexene purity", when the performance parameter related to olefin oligomerization is 1-hexene purity: [1] the one or more ground-state model structures GS derived from one or more first-trained heteroatom ligand-metal compound complexes. A1 ...GS Ap It may include or may be selected independently from GS I -VI, GS I -VIII, GS I -IX, GS I -X, GS I -XI or any combination thereof; [2] the multiple transition state model structures TS derived from one or more first-trained heteroatom ligand-metal compound complexes. A1 TS A2 ...TS Am It may include or may be selected independently from 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; [3] one or more ground-state model structures GS derived from the first target heteroatom ligand-metal compound complex. B1 ...GSBp It may include or may be selected independently from GS I -VI, GS I -VIII, GS I -IX, GS I -X, GS I -XI or any combination thereof; and / or [4] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm It may include or may be selected from 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 the purity of 1-hexene can be based on the mass ratio of 1-hexene to the total amount of other (non-1-hexene) C6 products, calculated as ln[(mass of 1-hexene) / (mass of non-1-hexene C6)] compared to ΔΔG[TS(1-hexene)-TS(non-1-hexene C6)].

[0435] Another method for determining the purity of 1-hexene may require separate determination. Figure 6 The 1-hexene activity / yield of each 1-hexene route was determined individually. Figure 6 The activity / productivity of each C6 impurity generated by the route, and the percentage of the sum of all 1-hexene activities / productivity to the sum of all 1-hexene activities / productivity plus the sum of all C6 impurity activities / productivity. Figure 6 The activity / productivity of each l-hexene production route and each C6 impurity production route can be determined by the methods described herein (e.g., via determining...). Figure 6 The activity / productivity is calculated / determined / estimated by using the conversion frequencies of all 1-hexene production routes and all C6 production routes.

[0436] Regarding “1-octene purity”, when the performance parameter related to the olefin oligomerization reaction is 1-octene purity: [1] the one or more ground-state model structures GS derived from one or more first-trained heteroatom ligand-metal compound complexes. A1 ...GS Ap It may include or may be selected independently from GSI -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 It may include or may be selected independently from GS T -VII, GS T -XII, GS T -XIII or any combination thereof. When one or more of the performance parameters include or are selected from 1-octene purity, they can be determined based on the mass ratio of 1-octene to the total amount of other (non-1-octene) C8 products and calculated by comparing ln[(mass of 1-octene) / (mass of non-1-octene C8)] with ΔG[TS(1-octene)-TS(non-1-octene C8)].

[0437] Check Figure 5C and Figure 6 It can be seen that each addition of the fourth ethylene does not lead to the formation of 1-octene. For example, in Figure 6 As can be seen, ethylene can complex to a) GS-IX to form 1) methylenecyclopentane via the GS-IX / TS-X / GS-X / TS-XII pathway, and / or 2) methylcyclopentane and ethylene via the GS-IX / TS-X / GS-X / TS-XI pathway, and / or complex to b) GS-VI to form 1-hexene and ethane via the GS-VI / TS-XIII / GS-XI / TS-XIV pathway. Therefore, these pathways lead to low efficiency of the fourth ethylene addition in olefin tetramerization. Thus, a specific parameter associated with olefin oligomerization could be the efficiency of the fourth ethylene addition to 1-octene.

[0438] The efficiency of 1-octene by the fourth ethylene addition can be expressed as the number of moles of 1-octene produced 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 via the fourth ethylene addition. Any one or more of the moles of methylenecyclopentane, methylcyclopentane, and 1-hexene can be used to calculate the efficiency of 1-octene by the fourth ethylene addition and can be determined based on the relative moles of methylenecyclopentane, methylcyclopentane, or 1-hexene produced via the fourth ethylene addition.

[0439] The methods described herein can be used to determine the efficiency of 1-octene in the fourth ethylene addition. A particular non-limiting method replaces the molar numbers of 1-octene and methylenecyclopentane, methylcyclopentane, and / or 1-hexene with their activity / productivity calculated using the conversion frequencies described herein. In this method, 1) the molar number of 1-octene is replaced with the calculated activity / productivity determined by conversion frequency calculations using all ground and transition states in the GS-II / GS-III / GS-IV / GS-VI / TS-IV / GS-V / TS-IV / GS-VII / TS-V pathways, and 2) the molar number of methylenecyclopentane is replaced with the calculated activity / productivity determined by conversion frequency calculations using all ground and transition states in the GS-II / GS-III / GS-IV / GS-VI / TS-VI / GS-VIII / TS-VIII / GS-IX / TS-X / GS-X / TS-XII pathways. Activity / productivity, 3) the molar number of methylcyclopentane is replaced with the calculated activity / productivity determined by conversion frequencies using all ground and transition states in the GS-II / GS-III / GS-IV / GS-VI / TS-VI / GS-VIII / TS-VIII / GS-IX / TS-X / GS-X / TS-XI pathways, and 4) the molar number of methylcyclopentane is replaced with the calculated activity / productivity determined by conversion frequencies using all ground and transition states in the GS-II / GS-III / GS-IV / GS-VI / TS-XIII / GS-XI / TS-XIV pathways. If other significant fourth ethylene additions producing products other than 1-octene are found, they can be added to the determination of the efficiency of the fourth ethylene addition to 1-octene, and the amount of additional fourth ethylene additions can be determined by the calculated activity / productivity determined by conversion frequencies using all ground and transition states in the appropriate reaction pathway.

[0440] On the one hand, understanding the detailed parameters affecting the selectivity of olefin oligomerization is a goal that can lead to heteroatom ligand-metal compound complexes producing a higher proportion of 1-octene when needed, and heteroatom ligand-metal compound complexes producing a higher proportion of 1-hexene when needed. In this regard, the evolution of the ground state that produces 1-hexene (ethylene trimer), and the transition state that forms from these ground states to eliminate 1-hexene or add another ethylene molecule to form the transition state that produces 1-octene (ethylene tetramer), is of great interest. In this aspect of selectivity (C6 / C8 ratio): [1] the multiple transition state model structures TS derived from one or more first training heteroatom ligand-metal compound complexes A1 TS A2 ...TS Am It may include methods for adding olefins to ground-state model structures GS I-VI to form the ground state model structure GS I -VII transition state; and / or [2] the multiple transition state model structures TS derived from one or more first target heteroatom ligand-metal compound complexes. B1 TS B2 ...TS Bm This may include methods for adding olefins (e.g., ethylene) to the ground-state model structure GS. T -VI to form the ground state model structure GS T -VII transition state. Also in this aspect of selectivity (C6 / C8 ratio): [1] the multiple transition state model structures TS derived from the first training heteroatom ligand-metal compound complex. A1 TS A2 ...TS Am It can include the transition state TS I -IV; and / or [2] the multiple transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm It can include the transition state TS T -IV.

[0441] Regarding this aspect of selectivity (C6 / C8 ratio): [1] the multiple transition state model structures TS derived from one or more first-trained heteroatom ligand-metal compound complexes A1 TS A2 ... Am It can include the GS for the ground state model structure I -VI elimination of β-H induces a transition state for 1-hexene and / or is used to transform the ground-state model structure GS. I -VII elimination of β-H, resulting in a transition state for the production of 1-octene; and / or [2] the multiple transition state model structures TS derived from one or more first-target heteroatom ligand-metal compound complexes. B1 TS B2 ...TS Bm It can include the GS for the ground state model structure T -VI elimination of β-H induces a transition state for 1-hexene and / or is used to transform the ground-state model structure GS. T -VII Elimination of β-H results in a transition state that produces 1-octene. Regarding the elimination of β-H from the above ground-state model structures: [1] the multiple transition-state model structures TS derived from the first training heteroatom ligand-metal compound complex. A1 TS A2 ...TS Am It can include TSI -III; [2] The multiple transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm It can include TS T -III; [3] The multiple transition state model structures TS derived from the first training heteroatom ligand-metal compound complex. A1 TS A2 ...TS Am It can include TS I -V; and / or [4] the multiple transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm It can include TS T -V. Furthermore, for eliminating β-H from the ground-state model structure, it is used to eliminate GS from the ground-state model structure. I -VI and / or GS T -VI elimination of β-H, the transition state model for the formation of 1-hexene can be TS I -III and / or TS I -III; and / or used to extract from the ground state model structure GS I -VII and / or GS T -VII elimination of β-H, the transition state model for the generation of 1-octene can be TS I -V and / or TS I -V.

[0442] The disclosed method includes an iterative process that repeats steps (a)-(f) of the above method one or more times, using the n output variables O of the first target heteroatom ligand-metal compound complex. 1 O 2 ...O n The quantitative value is derived from n new input variables I used for olefin oligomerization, comprising one or more second-trained heteroatom ligand-metal compound complexes containing second-trained heteroatom ligands. 1.1 I 2.1 ...I n.1 The input dataset is evaluated against a machine learning model to generate a second target heteroatom ligand-metal compound complex containing a second target heteroatom ligand, wherein the second target heteroatom ligand-metal compound complex is characterized by new n output variables O 1.1 O 2.1 ...O n.1The output dataset contains quantitative values ​​and performance parameter values ​​for one or more second-target heteroatom ligand-metal compound complexes.

[0443] On one hand, when the chromium heteroatom ligand moiety is independently selected from NPFCrM-1, NPACrM-1, GuCrM-1, GuCrM-2, GuCrM-3, GuCrM-4, GuCrM-5, or HCPACrM-1, the step of generating the second target heteroatom ligand-metal compound complex may include:

[0444] (a) Adjust one or more n input variables I 1 I 2 ...I n or I 1.1 I 2.1 ...I n.1 The quantitative value is close to the corresponding n output variables O in any first training heteroatom ligand-metal compound complex containing the chromium heteroatom ligand moiety. 1 O 2 ...O n Or O 1.1 O 2.1 ...O n.1 The value of the chromium heteroatom ligand is independently selected from NPFCrM-1, NPACrM-1, GuCrM-1, GuCrM-2, GuCrM-3, GuCrM-4, GuCrM-5, or HCPACrM-1, and the adjustment is made in the following manner:

[0445] [1] Independently increase or decrease 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 4S One or more spatial volumes;

[0446] [2] Independently change the group R 1 R 2 L 12r R 2a R 2b L 12 L 23 L 22 R 3 R 4 R 5and L 45 One or more of them are affected by the induced electronic effects of one or more +I substituents or one or more -I substituents;

[0447] [3] Independently increase or decrease the saturation of one or more of the organic or suborganic groups;

[0448] [4] Increase or decrease the polarity of the solvent used for olefin oligomerization; or

[0449] [5] Any combination thereof;

[0450] and

[0451] (b) Based on at least one adjusted n input variables from step (a), generate a second target heteroatom ligand-metal compound complex for olefin oligomerization and containing a second target heteroatom ligand.

[0452] In another aspect, when the chromium heteroatom ligand moiety is independently selected from NRNCrM-1, PRPCrM-1, SRSCrM-1, PNPCrM-1, NNRNRNCrM-1, PPRPCrM-1, SRRNSCrM-1, PRNRPCrM-1, or NRPRNCrM-1, the step of generating the second target heteroatom ligand-metal compound complex may include:

[0453] (a) Adjust one or more n input variables I 1 I 2 ...I n Or I 1.1 I 2.1 ...I n.1 The quantitative value is close to the corresponding n output variables O in any first training heteroatom ligand-metal compound complex containing the chromium heteroatom ligand moiety. 1 O 2 ...O n Or O 1.1 O 2.1 ...O n.1 The value of the chromium heteroatom ligand is independently selected from NRNCrM-1, PRPCrM-1, SRSCrM-1, PNPCrM-1, NNRNRNCrM-1, PPRPCrM-1, SRRRSCrM-1, PRNRPCrM-1, or NRPRNCrM-1, and the adjustment is made in the following manner:

[0454] [1] Independently increase or decrease the group R 1s R 2s R 5s R 11s R12s R 13s R 14s L 1s L 3s L 4s L 1sr L 1sr L 12sr and L 34sr One or more spatial volumes;

[0455] [2] Independently change 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 One or more of them are affected by the induced electronic effects of one or more +I substituents or one or more -I substituents;

[0456] [3] Independently increase or decrease the saturation of one or more of the organic or suborganic groups;

[0457] [4] Increase or decrease the polarity of the solvent used for olefin oligomerization; or

[0458] [5] Any combination thereof;

[0459] and

[0460] (b) Based on at least one adjusted n input variables from step (a), generate a second target heteroatom ligand-metal compound complex for olefin oligomerization and containing a second target heteroatom ligand.

[0461] Those skilled in the art will understand how independently i...

Claims

1. A method for designing heteroatom ligand-metal compound complexes for olefin oligomerization, the method comprising: (a) Select n Input variable I 1 I 2 ...I n Each input variable corresponds to one or more ground state model structures GS. A1 ...GS Ap and multiple transition state model structures TS associated with the one or more ground state model structures. A1 TS A2 ...TS Am The structural or electronic properties, where each of n, p, and m is an integer. The one or more ground state model structures GS A1 ...GS Ap Each of the multiple transition state model structures TS A1 TS A2 ...TS Am Each of them is generated from one or more first-trained heteroatom ligand-metal compound complexes, and each complex contains a first-trained heteroatom ligand; (b) For the ground state model structure GS A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am Each of them, for each n Input variable I 1 I 2 ...I n Allocate quantitative values; (c) The ground state model structure GS is determined by at least one processor of the device. A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am The relative energy of each of them; (d) Generate machine learning models to incorporate each n Input variable I 1 I 2 ...I n The quantitative value and the ground state model structure GS A1 ...GS Ap Each of them and the transition state model structure TS A1 TS A2 ...TS Am The relative energies of each of them are interconnected; (e) Using the machine learning model, determine the n Input variable I 1 I 2 ...I n One or more of the following relationships: [1] the ground state model structure GS A1 ...GS Ap One of the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between at least one of them [ΔG(TS-GS) or ΔΔG(TS-GS)] or [2] the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between any two or more of them [ΔG(TS-TS) or ΔΔG(TS-TS)]; (f) Based on the relationship identified in step (e), generate the output of the machine learning model comprising a first target heteroatom ligand-metal compound complex, the complex being used for olefin oligomerization and comprising the first target heteroatom ligand, wherein the first target heteroatom ligand-metal compound complex is characterized by: n Output variables O 1 O 2 ...O n Each output variable has a corresponding ground state model structure GS. B1 ...GS Bx Or multiple transition state model structures TS associated with one or more ground state model structures. B1 TS B2 ...TS By The quantitative value of any structural or electronic property of x and y, where each of x and y is an integer. The one or more ground state model structures GS B1 ...GS Bx Each of the multiple transition state model structures TS B1 TS B2 ...TS By Each of these is formed from the first target heteroatom ligand-metal compound complex, and each complex contains the first target heteroatom ligand. The above n Output variables O 1 O 2 ...O n New ones that are reused as the machine learning model n Input variable I 1.1 I 2.1 ...I n.1 ; (g) For the one or more first training heteroatom ligand-metal compound complexes and the first target heteroatom ligand-metal compound complexes, identify one or more performance parameters related to the olefin oligomerization reaction and the values ​​of the performance parameters; and (h) Using the first target heteroatom ligand-metal compound complex n Output variables O 1 O 2 ...O n The quantitative value is used as the new n Input variable I 1.1 I 2.1 ...I n.1 Repeat steps (a)-(f) once or more with the input dataset, the new n Input variable I 1.1 I 2.1 ...I n.1 Derived from one or more second-trained heteroatom ligand-metal compound complexes used for olefin oligomerization and containing a second trained heteroatom ligand, the input dataset is fed into the machine learning model to generate a second-target heteroatom ligand-metal compound complex containing a second target heteroatom ligand, wherein the second-target heteroatom ligand-metal compound complex is characterized by novel... n Output variables O 1.1 O 2.1 ...O n.1 The output dataset contains quantitative values ​​and has one or more second target heteroatom ligand-metal compound complex performance parameter values.

2. The method of claim 1, further comprising the following step: (i) [1] Synthesize the first target heteroatom ligand and / or the second target heteroatom ligand; or [2] Synthesize the first target heteroatom ligand and / or the second target heteroatom ligand, and then synthesize the first target heteroatom ligand-metal compound complex or the second target heteroatom ligand-metal compound complex.

3. The method of claim 2, further comprising the following step: (j) The olefin oligomerization reaction is carried out by: [1] contacting the first target heteroatom ligand or the second target heteroatom ligand, the metal compound, the organometallic compound and the olefin; Or [2] contact the first target heteroatom ligand-metal compound complex or the second target heteroatom ligand-metal compound complex, organometallic compound and olefin.

4. The method of claim 1, wherein the determination in step (e) of the n Input variable I 1 I 2 ...I n The one or more mentioned above are identified based on the following large percentage changes: [1] the one or more ground state model structures GS A1 ...GS Ap Any one of the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference between at least one of them [ΔG(TS-GS) or ΔΔG(TS-GS)] or [2] the multiple transition state model structures TS A1 TS A2 ...TS Am The energy difference [ΔG(TS-TS) or ΔΔG(TS-TS)] between any two or more of them, for the n Input variable I 1 I 2 ...I n Each percentage change of one or more of the above will affect ΔG(TS-GS), ΔΔG(TS-GS), or ΔΔG(TS-TS).

5. The method of claim 1, wherein the one or more first trained heteroatom ligand-metal compound complexes have chemical formulas independently selected from: [(HetLig)CrX q L r ] 3-q (A); where: HetLig represents one or more of the first training heteroatom ligands; X is an anionic ligand, and q It is an integer; L is a neutral ligand, and r It is an integer. Any two or more of the X and L ligands can be linked to form a polydentate ligand; and Each of the selected n Input variable I 1 I 2 ...I n , corresponding to the one or more ground state model structures GS A1 ...GS Ap Any of the ground state model structures TS associated with one or more ground state model structures of equation (A) A1 TS A2 ...TS Am The structural or electronic properties of any one of them.

6. The method of claim 1, wherein the derivatives are derived from one or more first trained heteroatom ligand-metal compound complexes (GS). I The one or more ground state model structures GS A1 ...GS Ap And one or more first target heteroatom ligand-metal compound complexes (GS) derived from the first target heteroatom ligand-metal compound complexes. T The one or more ground state model structures GS B1 ...GS Bx Selected independently from: in: HetLig represents the one or more first training heteroatom ligands or the one or more first target heteroatom ligands, and GS X It is the first training heteroatom ligand-metal compound complex (GS) I ) or the first target heteroatom ligand-metal compound complex (GS) T ).

7. The method of claim 6, wherein the derivative of one or more first trained heteroatom ligand-metal compound complexes (TS) I The multiple transition state model structures TS A1 TS A2 ...TS Am And one or more first target heteroatom ligand-metal compound complexes (TS) derived from the first target heteroatom ligand-metal compound complexes. T The multiple transition state model structures TS B1 TS B2 ...TS By Selected independently from: in: HetLig represents the one or more first training heteroatom ligands or the one or more first target heteroatom ligands, and TS Y It is the first training heteroatom ligand-metal compound complex (TS) I ) or the first target heteroatom ligand-metal compound complex (TS) T ).

8. The method of claim 1, wherein any one of the one or more ground-state model structures and the plurality of transition-state model structures comprises a chromium heteroatom ligand moiety independently selected from: in: R 1 It is hydrogen or C1 to C 20 Organic groups; R 2 It is C1 to C 20 Organic groups; T represents oxygen or sulfur; R 2a and R 2b Independently, they are C1 to C 20 Organic groups; L 12 and L 23 Independently, it is C2 to C 20 Suborganic groups; L 22 It is C3 to C 20 Suborganic groups; R 3 It is hydrogen or C1 to C 20 Organic groups; and R 4 and R 5 Independently hydrogen or C1 to C 20 Organic groups; Where R 1 and R 2 Optional connections to form L 12r And L 12r It is C3 to C 30 Suborganic groups; Where R 4 and R 5 Optional connections to form L 45 And L 45 It is C4 to C 30 Suborganic groups; and in" " indicates any additional bonding required from the following: [1] derived from any one or more ground state model structures or any one of the plurality of transition state model structures of the one or more first training heteroatom ligand-metal compound complexes, or [2] derived from any one or more ground state model structures or any one of the plurality of transition state model structures of the one or more first target heteroatom ligand-metal compound complexes.

9. The method of claim 8, wherein: R 1 It is hydrogen, C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon groups; R 2 It is C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon groups; R 2a and R 2b Independently selected from C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon groups; L 12 and L 23 Independently selected from C2 to C 20 Hydroxyl groups or C2 to C 20 Heterohydrocarbon groups; L 22 It is C3 to C 20 Hydroxyl groups or C3 to C 20 Heterohydrocarbon groups; R 3 It is hydrogen, C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon groups; and R 4 and R 5 Independently selected from C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon groups; Where R 1 and R 2 Optional connections to form L 12r And L 12r It is C3 to C 20 Hydroxyl groups or C3 to C 20 Heterohydrocarbon groups; and Where R 4 and R 5 Optional connections to form L 45 And L 45 It is C4 to C 20 Hydroxyl groups or C4 to C 20 Heterohydrocarbon group.

10. The method of claim 8, wherein... n Input variable I 1 I 2 ...I n Includes or is selected from any one or more of the following variables: (a) Cr-P distance (Å); (b) Cr-N distance (Å); (c) Cr-R distance (Å) on α-C; (d) P-Cr-N angle (degrees); (e) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to the Cr atom or within the bonding distance of the Cr atom; (f) Cr-NC angle (degrees); (g) Distance outside the bag (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) Percentage of buried volume.

11. The method of claim 1, wherein any one of the one or more ground-state model structures and the plurality of transition-state model structures comprises a chromium heteroatom ligand moiety independently selected from: in: Each R 1s R 2s R 5s R 11s R 12s R 13s and R 14s Independently selected from hydrogen or C1 to C 20 Organic groups; Each L 1s L 3s and L 4s Independently selected from C2 to C 20 Suborganic groups; and Any two Together R 1s Optional connections to form L 11s And L 11s It is C3 to C 30 Suborganic groups; Any two Together R 2s Optional connections to form L 22s And L 22s It is C3 to C 30 Suborganic groups; any Together R 11s and R 12s Optional connections to form L 12s And L 12s It is C3 to C 30 Suborganic groups; any Together R 13s and R 14s Optional connections to form L 34s And L 34s It is C3 to C 30 Suborganic groups; in" " indicates any additional bonding required from the following: [1] derived from any one or more ground state model structures or any one of the plurality of transition state model structures of the one or more first training heteroatom ligand-metal compound complexes, or [2] derived from any one or more ground state model structures or any one of the plurality of transition state model structures of the one or more first target heteroatom ligand-metal compound complexes.

12. The method of claim 11, wherein: Each R 1s R 2s R 5s R 11s R 12s R 13s and R 14s Independently selected from hydrogen, C1 to C 20 Hydrocarbon group or C1 to C 20 heterohydrocarbon groups; Each L 1s L 3s and L 4s Independently selected from C2 to C 20 Hydroxyl groups or C2 to C 20 Heterohydrocarbon groups; Any two Together R 1s Optional connections to form L 11s And L 11s It is C2 to C 20 Hydroxyl groups or C2 to C 20 Heterohydrocarbon groups; Any two Together R 2s Optional connections to form L 22s And L 22s It is C2 to C 20 Hydroxyl groups or C2 to C 20 Heterohydrocarbon groups; any Together R 11s and R 12s Optional connections to form L 12s And L 12s It is C2 to C 20 Hydroxyl groups or C2 to C 20 Heterohydrocarbon groups; and any Together R 13s and R 14s Optional connections to form L 34s And L 34s L 22s and L 22sF It is C2 to C 20 Hydroxyl groups or C2 to C 20 Heterohydrocarbon group.

13. The method of claim 11, wherein... n Input variable I 1 I 2 ...I n Includes or is selected from any one or more of the following variables: (a) First, second, or third Cr-N distance (Å); (b) 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) C-Cr-N angle (degrees), where C is a non-heteroatom ligand carbon atom bonded to the Cr atom or within the 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 (Å) on α-C; (q) Distance outside the bag (Å); (r) Cr---α-C distance (Å); (s) Cr CHELPG (atomic charge); (t) Any P CHELPG (atomic charge); (u) Any N CHELPG (atomic charge); (v) Any chelated Cr-NCC dihedral angle (degrees); (w) Any chelated Cr-PCC dihedral angle (degrees); (x) Any chelated Cr-SCC dihedral angle (degrees); or (y) Percentage of buried volume.

14. The method of claim 1, wherein the one or more performance parameters associated with the olefin oligomerization reaction are 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 plus 1-octene; (g) trimerization selectivity for 1-hexene; (h) tetramerization selectivity for 1-octene; (i) 1-octene efficiency of the fourth ethylene addition; or any combination thereof.

15. The method of claim 7, wherein: (a) [1] one or more ground-state model structures GS derived from one or more first-trained heteroatom ligand-metal compound complexes A1 ...GS Ap Includes or independently selected from GS I -I, GS 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 TS A2 ...TS Am Includes or is selected independently from TS I -I、TS I -II、TS I -III, TS I -IV、TS I -V or any combination thereof; (b) [1] One or more ground-state model structures GS derived from the first target heteroatom ligand-metal compound complex. B1 ...GS Bp Includes or independently selected from GS T -I, GS T -II, GS T -III, GS T -IV, GS T -V、GS T -VI, GS T -VII 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 TS B2 ...TS Bm Includes or is selected independently from TS T -I、TS T -II、TS T -III, TS T -IV、TS T -V or any combination thereof; and (c) The performance parameters associated with the olefin oligomerization reaction are the heteroatom ligand-metal compound complex 1-hexene production rate, 1-octene production rate, or the total production rate of 1-hexene and 1-octene.

16. The method of claim 7, wherein: (a) [1] one or more ground-state model structures GS derived from one or more first-trained heteroatom ligand-metal compound complexes A1 ...GS Ap Including GS I -VI and [2] derived from the multiple transition state model structures TS of one or more first-trained heteroatom ligand-metal compound complexes A1 TS A2 ...TS Am Including TS I -III and TS I -IV, (b) [1] One or more ground-state model structures GS derived from the first target heteroatom ligand-metal compound complex. B1 ...GS Bp Including GS T -VI, and [2] the multiple transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm Including TS T -III and TS T -IV; as well as (c) The performance parameter associated with the olefin oligomerization reaction is the C6 / C8 ratio.

17. The method of claim 7, wherein: (a) [1] one or more ground-state model structures GS derived from one or more first-trained heteroatom ligand-metal compound complexes A1 ...GS Ap Includes or independently selected from GS I -VI, GS I -VIII, GS I -IX, GS I -X, GS I -XI or any combination thereof, and [2] derived from the plurality of transition state model structures TS of one or more first training heteroatom ligand-metal compound complexes. A1 TS A2 ...TS Am Includes or is selected independently from 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] One or more ground-state model structures GS derived from the first target heteroatom ligand-metal compound complex. B1 ...GS Bp Includes or independently selected from GS I -VI, GS I -VIII, GS I -IX, GS I -X, GS I -XI or any combination thereof, and [2] multiple transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm Includes or selected from 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 (c) The performance parameter associated with the olefin oligomerization reaction is the purity of 1-hexene.

18. The method of claim 7, wherein: (a) [1] one or more ground-state model structures GS derived from one or more first-trained heteroatom ligand-metal compound complexes A1 ...GS Ap Includes or independently selected from GS I -VII, GS I -XII, GS I -XIII or any combination thereof, and [2] derived from one or more ground-state model structures GS of the first target heteroatom ligand-metal compound complex. B1 ...GS Bp Includes or independently selected from GS T -VII, GS T -XII, GS T -XIII or any combination thereof; and (b) The performance parameter associated with the olefin oligomerization reaction is the purity of 1-octene.

19. The method of claim 7, wherein: (a) [1] The multiple transition state model structures TS derived from one or more first-trained heteroatom ligand-metal compound complexes A1 TS A2 ...TS Am Includes the addition of the olefin to the ground-state model structure GS I -VI to form the ground state model structure GS I -VII transition state; and / or [2] the multiple transition state model structures TS derived from one or more first target heteroatom ligand-metal compound complexes. B1 TS B2 ...TS Bm Includes the addition of the olefin to the ground-state model structure GS T -VI to form the ground state model structure GS T -VII transition state; or (b) [1] The plurality of transition state model structures TS derived from the first training heteroatom ligand-metal compound complex A1 TS A2 ...TS Am Including the transition state TS I -IV; and / or [2] the plurality of transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm Including the transition state TS T -IV.

20. The method of claim 7, wherein: (a) [1] The multiple transition state model structures TS derived from one or more first-trained heteroatom ligand-metal compound complexes A1 TS A2 ...TS Am Includes the use of ground state model structure GS I -VI elimination of β-H induces a transition state for 1-hexene and / or is used to transform the ground-state model structure GS. I -VII elimination of β-H, resulting in a transition state for the production of 1-octene; and / or [2] the multiple transition state model structures TS derived from one or more first-target heteroatom ligand-metal compound complexes. B1 TS B2 ...TS Bm Includes the use of ground state model structure GS T -VI elimination of β-H induces a transition state for 1-hexene and / or is used to transform the ground-state model structure GS. T -VII eliminates β-H, inducing a transition state for the formation of 1-octene; and (b) [1] The plurality of transition state model structures TS derived from the first training heteroatom ligand-metal compound complex A1 TS A2 ...TS Am Including TS I -III or TS I -V; and / or [2] the multiple transition state model structures TS derived from the first target heteroatom ligand-metal compound complex. B1 TS B2 ...TS Bm Including TS T -III or TS T -V.

21. The method of claim 1, wherein for 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 Each of the multiple transition state model structures TS A1 TS A2 ...TS Am Each of them, assigned to each n Input variable I 1 I 2 ...I n The quantitative values ​​are assigned based on calculated values, measured values, or estimated values, or any combination thereof.

22. The method of claim 1, wherein the step of generating the second target heteroatom ligand-metal compound complex comprises: (a) Adjust one or more n Input variable I 1 I 2 ...I n or I 1.1 I 2.1 ...I n.1 The quantitative value is close to the corresponding value in any first-trained heteroatom ligand-metal compound complex containing the chromium heteroatom ligand moiety. n Output variables O 1 O 2 ...O n Or O 1.1 O 2.1 ...O n.1 The value of the chromium heteroatom ligand is independently selected from NPFCrM-1, NPACrM-1, GuCrM-1, GuCrM-2, GuCrM-3, GuCrM-4, GuCrM-5, or HCPACCrM-1. in: R 1 It is hydrogen or C1 to C 20 Organic groups; R 2 It is C1 to C 20 Organic groups; T represents oxygen or sulfur; R 2a and R 2b Independently, they are C1 to C 20 Organic groups; L 12 and L 23 Independently, it is C2 to C 20 Suborganic groups; L 22 It is C3 to C 20 Suborganic groups; R 3 It is hydrogen or C1 to C 20 Organic groups; and R 4 and R 5 Independently hydrogen or C1 to C 20 Organic groups; Where R 1 and R 2 Optional connections to form L 12r And L 12r It is C3 to C 30 Suborganic groups; Where R 4 and R 5 Optional connections to form L 45 And L 45 It is C4 to C 30 Suborganic groups; and in" " indicates any additional bonding required from the following: [1] derived from any of the one or more ground-state model structures or any of the multiple transition-state model structures of the one or more first training heteroatom ligand-metal compound complexes, or [2] derived from any of the one or more ground-state model structures or any of the multiple transition-state model structures of the one or more first target heteroatom ligand-metal compound complexes, The adjustments were made in the following manner: [1] Independently increase or decrease 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 One or more spatial volumes; [2] Independently change 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 One or more of them are subject to one or more +I Substituents or one or more -I The induced electronic effect of substituents; [3] Independently increase or decrease the saturation of one or more of the organic or suborganic groups; [4] Increase or decrease the polarity of the solvent used for olefin oligomerization; or [5] Any combination thereof; and (b) Based on at least one adjusted [from step (a)] n One input variable is used to generate a second target heteroatom ligand-metal compound complex for olefin oligomerization and containing a second target heteroatom ligand.

23. The method of claim 1, wherein the step of generating the second target heteroatom ligand-metal compound complex comprises: (a) Adjust one or more n Input variable I 1 I 2 ...I n or I 1.1 I 2.1 ...I n.1 The quantitative value is close to the corresponding value in any first-trained heteroatom ligand-metal compound complex containing the chromium heteroatom ligand moiety. n Output variables O 1 O 2 ...O n Or O 1.1 O 2.1 ...O n.1 The value of the chromium heteroatom ligand is independently selected from NRNCrM-1, PRPCrM-1, SRSCrM-1, PNPCrM-1, NNRNRNCrM-1, PPRPRPCrM-1, SRRRSCrM-1, PRNRPCrM-1, or NRPRNCrM-1. in: Each R 1s R 2s R 5s R 11s R 12s R 13s and R 14s Independently selected from hydrogen or C1 to C 20 Organic groups; Each L 1s L 3s and L 4s Independently selected from C2 to C 20 Suborganic groups; and Any two Together R 1s Optional connections to form L 11s And L 11s It is C3 to C 30 Suborganic groups; Any two Together R 2s Optional connections to form L 22s And L 22s It is C3 to C 30 Suborganic groups; any Together R 11s and R 12s Optional connections to form L 12s And L 12s It is C3 to C 30 Suborganic groups; any Together R 13s and R 14s Optional connections to form L 34s And L 34s It is C3 to C 30 Suborganic groups; in" " indicates any additional bonding required from the following: [1] derived from any of the one or more ground-state model structures or any of the multiple transition-state model structures of the one or more first training heteroatom ligand-metal compound complexes, or [2] derived from any of the one or more ground-state model structures or any of the multiple transition-state model structures of the one or more first target heteroatom ligand-metal compound complexes, The adjustments were made in the following manner: [1] Independently increase or decrease 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 One or more spatial volumes; [2] Independently change 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 One or more of them are subject to one or more +I Substituents or one or more -I The induced electronic effect of substituents; [3] Independently increase or decrease the saturation of one or more of the organic or suborganic groups; [4] Increase or decrease the polarity of the solvent used for olefin oligomerization; or [5] Any combination thereof; and (b) Based on at least one adjusted [from step (a)] n One input variable is used to generate a second target heteroatom ligand-metal compound complex for olefin oligomerization and containing a second target heteroatom ligand.

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