Bis(arene)metal complexes and related methods

Abstract

Methods for preparing and purifying bis(arene) metal complexes are provided. The methods may include contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture containing an intermediate complex. The methods may include contacting the intermediate complex with a second metal component in a reaction mixture containing a second solvent to form a reaction mixture containing the bis(arene) metal complex. The methods may include contacting the reaction mixture containing the bis(arene) metal complex with a separation medium to obtain a product. Bis(arene) metal complexes are also provided.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates to the synthesis and purification of bis(arene) metal complexes, as well as related compositions and methods. [Background technology]

[0002] The synthesis and purification of organometallic compounds presents many challenges. Organometallic compounds are often produced in reaction mixtures containing mixed ligand complexes. Due to their similar molecular weights, these organometallic compounds cannot be easily separated and purified. Organometallic compounds are also often produced in low yields, which presents problems with scaling up the process for commercial production. Summary of the Invention

[0003] Some embodiments of the present disclosure relate to a method, in some embodiments, the method includes one or more of the following: contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture including an intermediate complex; contacting the intermediate complex with a second metal component in a reaction mixture including a second solvent to form a reaction mixture including a bis(arene) metal complex; and obtaining a product.

[0004] Some embodiments of the present disclosure relate to a method. In some embodiments, the method includes one or more of the following: contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture containing an intermediate complex; contacting the intermediate complex with a second metal component in a reaction mixture containing a second solvent to form a reaction mixture containing a bis(arene) metal complex; and contacting the reaction mixture containing the bis(arene) metal complex with a separation medium to obtain a product. In some embodiments, the product contains a purified bis(arene) metal complex and less than 10% impurities.

[0005] Some embodiments of the present disclosure relate to a method, in some embodiments, the method includes one or more of the following steps: contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture including an intermediate complex; and contacting the intermediate complex with a second metal component in a reaction mixture including a second solvent to form a reaction mixture including a bis(arene) metal complex.

[0006] Some embodiments of the present disclosure relate to a method, in some embodiments, the method includes one or more of the following: contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture comprising an intermediate complex; contacting the intermediate complex with a second metal component in a reaction mixture comprising a second solvent to form a reaction mixture comprising a bis(arene) metal complex; and performing a post-synthesis aqueous extraction to purify the reaction mixture and obtain a product.

[0007] Some embodiments of the present disclosure relate to methods. In some embodiments, the methods include one or more of the following steps: obtaining a reaction mixture containing a bis(arene) metal complex and at least one impurity; and contacting the reaction mixture containing the bis(arene) metal complex with a separation medium to obtain a product. In some embodiments, the product comprises a purified bis(arene) metal complex. In some embodiments, the product contains less of the at least one impurity, by weight, than the reaction mixture containing the bis(arene) metal complex.

[0008] Some embodiments of the present disclosure include a compound of the formula: TIFF2025529358000002.tif52170 [wherein M is Mo, Wo or Cr; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R 3, R 4 , R 5 and R 6 may be linked to form a 6-membered aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 two of which may be linked to form a six-membered aryl] The present invention relates to a composition comprising a bis(arene) metal complex of the formula:

[0009] Some embodiments of the present disclosure are herein described, by way of example only, with reference to the accompanying drawings. With specific reference now to the drawings in detail, it is emphasized that the illustrated embodiments are given by way of example and are intended as an illustrative discussion of embodiments of the present disclosure. In this regard, the description taken together with the drawings will make apparent to those skilled in the art how embodiments of the present disclosure may be practiced. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 depicts a flowchart of a non-limiting embodiment of a method according to some embodiments. [Figure 2] FIG. 2 depicts a flowchart of a non-limiting embodiment of a method according to some embodiments. [Figure 3] FIG. 3 depicts a schematic of a non-limiting embodiment of a reaction scheme, according to some embodiments. [Figure 4] 4A-4B represent 1H NMR spectra after (FIG. 3A) and before (FIG. 3B) passing the solution through a column containing neutral alumina, according to some embodiments. [Figure 5]5A-5B represent 27Al NMR spectra after (FIG. 4A) and before (FIG. 4B) passing a solution through a column containing neutral alumina, according to some embodiments. [Figure 6] 6A-6C show stacked 1H NMR spectra of the crude product, according to some embodiments. [Figure 7] 7A-7B show 1H NMR of the crude product after aluminum reduction and after sequential magnesium reduction, according to some embodiments. [Figure 8] 8A-8B show the 27Al NMR of the crude product after aluminum reduction and after sequential magnesium reduction, according to some embodiments. [Figure 9] FIG. 9 depicts a schematic of a non-limiting embodiment of a reaction scheme, according to some embodiments. [Figure 10] FIG. 10 shows a thermogravimetric analysis (“TGA”) of the product after post-synthesis aqueous extraction, according to some embodiments. [Figure 11] FIG. 11 shows a TGA of a post-synthesis aqueous extraction, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0011] Among the benefits and improvements disclosed, other objects and advantages of the present disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. While detailed embodiments of the present disclosure are disclosed herein, it should be understood that the disclosed embodiments are merely exemplary of the present disclosure, which may be embodied in various forms. Furthermore, each of the examples given with respect to various embodiments of the present disclosure are intended to be illustrative, not limiting.

[0012] Any prior patents and publications referenced herein are incorporated by reference in their entirety.

[0013] Throughout this specification and claims, the following terms take on the meanings expressly associated therewith unless the context clearly dictates otherwise. As used herein, the phrases "in one embodiment," "in one embodiment," and "in some embodiments" do not necessarily refer to the same embodiment, but may. Additionally, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, but may. It is intended that all embodiments of the present disclosure be combinable without departing from the scope or spirit of the disclosure.

[0014] As used herein, the term "based on" is not exclusive and allows for based on additional unrecited factors unless the context clearly dictates otherwise. Additionally, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0015] As used herein, the term "alkyl" refers to a hydrocarbon chain group having 1 to 30 carbon atoms. The alkyl may be attached via a single bond. An alkyl having n carbon atoms is referred to as "C n For example, "C alkyl" can include n-propyl and isopropyl. Alkyl having a range of carbon atoms, such as 1 to 30 carbon atoms, can be specified as C1-C 30 In some embodiments, alkyl is linear. In some embodiments, alkyl is branched. In some embodiments, alkyl is substituted. In some embodiments, alkyl is unsubstituted. In some embodiments, alkyl is C1-C 12 Alkyl, C1-C 11 Alkyl, C1-C 10The alkyl may comprise, consist of, consist essentially of, or be selected from the group consisting of at least one of alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C4 alkyl, C1-C3 alkyl, or any combination thereof. In some embodiments, the alkyl may comprise, consist essentially of, or be selected from the group consisting of at least one of methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, isobutyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, octyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0016] As used herein, the term "alkenyl" refers to a hydrocarbon chain group having 1 to 10 carbon atoms and at least one carbon-carbon double bond. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, 1-methylvinyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,3-pentadienyl, 2,4-pentadienyl, 1,4-pentadienyl, 3-methyl-2-butenyl, and the like. and at least one of 1,3-hexenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1,3-hexadienyl, 1,4-hexadienyl, 2-methylpentenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, 1,3-octadienyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1-undecenyl, oleyl, linoleyl, linolenyl, or any combination thereof.

[0017] As used herein, the term "alkynyl" refers to a hydrocarbon chain group having 1 to 10 carbon atoms and at least one carbon-carbon triple bond. Examples of alkynyl groups include, but are not limited to, at least one of ethynyl, propynyl, n-butynyl, n-pentynyl, 3-methyl-1-butynyl, n-hexynyl, methyl-pentynyl, or any combination thereof.

[0018] As used herein, the term "cycloalkyl" refers to a non-aromatic carbocyclic ring having 3 to 8 carbon atoms within the ring. This term includes monocyclic non-aromatic carbocyclic rings and polycyclic non-aromatic carbocyclic rings. Two or more cycloalkyls can be fused, bridged, or fused and bridged to give, for example, a polycyclic non-aromatic carbocyclic ring. In some embodiments, a cycloalkyl is selected from the group comprising, consisting of, consisting essentially of, or consisting of at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or any combination thereof.

[0019] As used herein, the term "arene" refers to a monocyclic or polycyclic aromatic hydrocarbon compound containing carbon and hydrogen atoms. In some embodiments, arenes have 6 to 8 carbon atoms, 6 to 10 carbon atoms, 6 to 12 carbon atoms, 6 to 15 carbon atoms, or 6 to 20 carbon atoms. The term "monocyclic," when used as a modifier, refers to arenes having a single aromatic ring structure. The term "polycyclic," when used as a modifier, refers to arenes having more than one aromatic ring structure, which may be fused, bridged, spiro, or otherwise linked ring structures. In some embodiments, the terms arene and aryl are used interchangeably.

[0020] Non-limiting examples of arenes include, but are not limited to, benzene, toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), t-butyltoluene (e.g., ot-butyltoluene, mt-butyltoluene, pt-butyltoluene), ethylmethylbenzene (e.g., 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene), 1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene, mesitylene, pseudocumene, durene, methylbenzene, dimethylbenzene, trimethylbenzene, ethyl At least one of benzene, diethylbenzene (e.g., 1,4-diethylbenzene), triethylbenzene, propylbenzene, butylbenzene, iso-butylbenzene, sec-butylbenzene, t-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenylene, dimethylnaphthalene, methylanthracene, 4,4′-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomer thereof, or any combination thereof may be included.

[0021] 1 is a flowchart of a method 100 for making a bis(arene) metal complex according to some embodiments. As shown in FIG. 1 , the method for making a bis(arene) metal complex includes one or more of the following steps: 102, contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture containing an intermediate complex; 104, contacting the intermediate complex with a second metal component in a reaction mixture containing a second solvent to form a reaction mixture containing a bis(arene) metal complex; and 106, contacting the reaction mixture containing the bis(arene) metal complex with a separation medium to obtain a product, wherein the product contains a purified bis(arene) metal complex and less than 10% impurities. It will be understood that method 100 can include any combination of at least two of steps 102, 104, 106, or any combination thereof.

[0022] In step 102, in some embodiments, the method 100 of making a bis(arene) metal complex includes contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture including an intermediate complex.

[0023] In another embodiment of the present disclosure, a method used to prepare a bis(arene) metal complex is shown in Figure 2. As shown in Figure 2, the method of preparing a bis(arene) metal complex includes one or more of the following steps: 202, contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture containing an intermediate complex; 204, contacting the intermediate complex with a second metal component in a reaction mixture containing a second solvent to form a reaction mixture containing a bis(arene) metal complex; and 206, performing a post-synthesis aqueous extraction to obtain a product, the product comprising a purified bis(arene) metal complex and less than 10% impurities. It will be understood that method 200 can include any combination of at least two of steps 202, 204, 206, or any combination thereof.

[0024] 1 and 2, the metal halide may be contacted at a first temperature. In some embodiments, the first temperature is the boiling point of the first solvent. In some embodiments, the first temperature is a temperature in the range of 50°C to 200°C. For example, in some embodiments, the first temperature is 50°C to 190°C, 50°C to 180°C, 50°C to 170°C, 50°C to 160°C, 50°C to 150°C, 50°C to 140°C, 50°C to 130°C, 50°C to 120°C, 50°C to 110°C, 50°C to 100°C, 50°C to 90°C, 50°C to 80°C, 50°C to 70°C, 60°C to 200°C, 70°C to 180°C, 50°C to 190°C, 5 ...200°C, 50°C to 200° The first temperature may be in the range of 80°C to 200°C, 80°C to 200°C, 90°C to 200°C, 100°C to 200°C, 110°C to 200°C, 120°C to 200°C, 130°C to 200°C, 140°C to 200°C, 150°C to 200°C, 160°C to 200°C, 170°C to 200°C, 180°C to 200°C, or any range or subrange therebetween. In some embodiments, the first temperature does not exceed the decomposition temperature of at least one of the metal halide, first metal component, aluminum halide, first solvent, intermediate complex, or any combination thereof.

[0025] The contacting can include, directly or indirectly, at least one of reducing, reacting, introducing, heating, or any combination thereof. In some embodiments, the contacting includes contacting at least one of a metal halide, a first metal component, an aluminum halide, a first solvent, or any combination thereof. In some embodiments, the contacting includes reacting at least one of a metal halide, a first metal component, an aluminum halide, a first solvent, or any combination thereof. In some embodiments, the contacting includes heating at least one of a metal halide, a first metal component, an aluminum halide, a first solvent, or any combination thereof. In some embodiments, the contacting includes reducing at least one of a metal halide, a first metal component, an aluminum halide, a first solvent, or any combination thereof.

[0026] The metal halide may include at least one of molybdenum (Mo), chromium (Cr), tungsten (W), or any combination thereof. In some embodiments, the metal halide includes at least one of MoCl, MoCl, MoCl, MoCl, MoCl, MoCl, or any combination thereof. In some embodiments, the metal halide includes at least one of CrCl, CrCl, or any combination thereof. In some embodiments, the metal halide includes at least one of WCl, WCl, WCl, WCl, WCl, WCl, or any combination thereof. In some embodiments, the metal halide includes at least one of MoCl, MoCl, MoCl, MoCl, MoCl, MoCl, CrCl, CrCl, WCl, WCl, WCl, WCl, WCl, or any combination thereof. In some embodiments, the metal halide includes at least one of WCl, WCl, WCl, WCl, WCl, WCl, WBr, WBr, WBr, WBr, WBr, WI, WI, WI, WI, WI, WI, MoCl, MoCl, MoCl, MoCl, MoBr, MoBr, MoBr, MoBr, MoI, MoI, MoI, MoI, or any combination thereof. In some embodiments, the metal halide includes a transition metal. In some embodiments, for example, the metal halide includes at least one of Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, or any combination thereof.

[0027] The first metal component may include a metal in solid form. For example, in some embodiments, the first metal component may include a metal in the form of a powder, particles, or tablets. In some embodiments, the metal of the first metal component includes at least one of Li, Na, K, Rb, Cs, Mg, Ca, Cd, Sr, Ba, Al, Ga, In, Zn, Sn, Fe, Ni, any alloy thereof, or any combination thereof. For example, in some embodiments, the first metal component includes at least one of Al, Ga, In, Zn, Sn, any alloy thereof, or any combination thereof. In some embodiments, the first metal component includes at least one of aluminum powder, magnesium powder, zinc powder, or any combination thereof. In some embodiments, the first metal component includes an alloy. For example, in some embodiments, the first metal component includes an aluminum-magnesium alloy powder. In some embodiments, the first metal component includes at least one of iron powder, nickel powder, or any combination thereof.

[0028] The first metal component can have an average particle size. Average particle size can refer to the average particle size of at least 50% of the first metal component. In some embodiments, the first metal component has an average particle size in the range of 50 nm to 100 μm. For example, in some embodiments, the first metal component has an average particle size in the range of 20 μm to 100 μm, 1 μm to 5 μm, 50 nm to 900 nm, or any combination thereof, or any range or subrange therebetween.

[0029] The aluminum halide may include at least one of aluminum chloride, aluminum bromide, aluminum iodide, or any combination thereof. Examples of aluminum chloride include, but are not limited to, at least one of AlCl2, AlCl3, hydrated forms thereof, and any combination thereof. Examples of aluminum bromide include, but are not limited to, at least one of AlBr2, AlBr3, hydrated forms thereof, and any combination thereof. Examples of aluminum iodide include, but are not limited to, at least one of AlI2, AlI3, hydrated forms thereof, and any combination thereof.

[0030] The first solvent can comprise an arene. For example, the first solvent can comprise an aromatic solvent. In some embodiments, the first solvent has the formula: TIFF2025529358000003.tif36170[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 two of which may be linked to form a six-membered aryl] This includes compounds of the formula:

[0031] In some embodiments, the first solvent has the formula: TIFF2025529358000004.tif32170[In the formula, R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 two of which may be linked to form a six-membered aryl] This includes compounds of the formula:

[0032] In some embodiments, the first solvent is free of heteroatoms, hi some embodiments, the first solvent is free of halides.

[0033] In some embodiments, the first solvent comprises at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, m-t-butyltoluene, pt-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene, mesitylene, pseudocumene, durene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, iso-butylbenzene, sec-butylbenzene, t-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenylene, dimethylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomer thereof, or any combination thereof. In some embodiments, the first solvent comprises alkyl-substituted benzene. In some embodiments, the first solvent comprises an aryl-substituted benzene. In some embodiments, the first solvent does not contain a heteroatom (e.g., as a ring atom of an arene). In some embodiments, the first solvent does not contain a halide substituent on the arene.

[0034] The resulting reaction mixture comprises an intermediate complex. In some embodiments, the intermediate complex has the formula: [bis(first solvent)metal] + [Aluminum halide] - In some embodiments, the metal is molybdenum (Mo), chromium (Cr), or tungsten (W). In some embodiments, the halide is chloride (Cl), bromide (Br), or iodide (I). In some embodiments, the intermediate complex is [bis(toluene)molybdenum] + [AlCl4] - Includes.

[0035] Referring to FIG. 1 , in step 104, in some embodiments, a method 100 of making a bis(arene) metal complex includes contacting the intermediate complex with a second metal component in a reaction mixture including a second solvent to form a reaction mixture including the bis(arene) metal complex.

[0036] The contacting can include, indirectly or directly, at least one of reducing, reacting, heating, introducing, or any combination thereof. In some embodiments, the contacting includes contacting at least one of the intermediate complex, the second metal component, the second solvent, a reaction mixture comprising the second solvent, or any combination thereof. In some embodiments, the contacting includes reacting at least one of the intermediate complex, the second metal component, the second solvent, a reaction mixture comprising the second solvent, or any combination thereof. In some embodiments, the contacting includes heating at least one of the intermediate complex, the second metal component, the second solvent, a reaction mixture comprising the second solvent, or any combination thereof. In some embodiments, the contacting includes reducing at least one of the intermediate complex, the second metal component, the second solvent, a reaction mixture comprising the second solvent, or any combination thereof.

[0037] The contacting can proceed at a second temperature. In some embodiments, the contacting includes reducing the intermediate complex at the second temperature. In some embodiments, the second temperature is in the range of 0°C to 150°C. In some embodiments, the second temperature is in the range of 10°C to 150°C, 20°C to 150°C, 30°C to 150°C, 40°C to 150°C, 50°C to 150°C, 60°C to 150°C, 70°C to 150°C, 80°C to 150°C, 90°C to 150°C, 100°C to 150°C, 110°C to 150°C, 120°C to 150°C, 130°C to 150°C, 140°C to 150°C, 150°C to 150°C, 160°C to 150°C, 170°C to 150°C, 180°C to 150°C, 190°C to 150°C, 200°C to 200°C, 210°C to 210°C, 220°C to 220°C, 230°C to 230°C, 240°C to 240°C, 250°C to 250°C, 260°C to 260°C, 270°C to 270°C, 280°C to 280°C, 290°C to 290°C, 300°C to 300°C, 310°C to 310°C, 320°C to 320°C, 330°C to 3 The temperature is any range or subrange of 0°C to 150°C, 0°C to 10°C, 0°C to 20°C, 0°C to 30°C, 0°C to 40°C, 0°C to 50°C, 0°C to 60°C, 0°C to 70°C, 0°C to 80°C, 0°C to 90°C, 0°C to 100°C, 0°C to 110°C, 0°C to 120°C, 0°C to 130°C, 0°C to 140°C, or 0°C to 150°C.

[0038] The second metal component may include a metal in solid form. For example, in some embodiments, the second metal component may include a metal in powder, particle, or tablet form. In some embodiments, the metal of the first metal component includes at least one of Li, Na, K, Rb, Cs, Mg, Ca, Cd, Sr, Ba, Al, Ga, In, Zn, Sn, Fe, Ni, any alloy thereof, or any combination thereof. For example, in some embodiments, the first metal component includes at least one of Al, Ga, In, Zn, Sn, any alloy thereof, or any combination thereof. In some embodiments, the second metal component includes at least one of aluminum powder, magnesium powder, zinc powder, or any combination thereof. In some embodiments, the second metal component includes an alloy. For example, in some embodiments, the second metal component includes an aluminum-magnesium alloy powder. In some embodiments, the second metal component includes at least one of iron powder, nickel powder, or any combination thereof. In some embodiments, the second metal component is the same as the first metal component. In some embodiments, the second metal component is different from the first metal component.

[0039] The second metal component can have an average particle size. Average particle size can refer to the average particle size of at least 50% of the second metal component. In some embodiments, the second metal component has an average particle size in the range of 50 nm to 100 μm. For example, in some embodiments, the second metal component has an average particle size in the range of 20 μm to 100 μm, 1 μm to 5 μm, 50 nm to 900 nm, or any combination thereof, or any range or subrange therebetween.

[0040] The second solvent may comprise an ether solvent. In some embodiments, the second solvent comprises a slowly evaporating solvent (reducing solvent). In some embodiments, the second solvent comprises a solvent having a boiling point sufficient to allow removal of the solvent under reduced pressure at a temperature below the sublimation temperature of the bis(arene) metal complex. For example, in some embodiments, the solvent has a boiling point below 150°C, below 140°C, below 130°C, below 120°C, or below 110°C. In some embodiments, the second solvent comprises a solvent having an ether bond. In some embodiments, the second solvent comprises at least one of tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane (DME), triglyme, diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, methyl tert-butyl ether (MTBE), or any combination thereof. In some embodiments, the second solvent comprises an 80 / 20 mixture of dimethoxyethane (DME) and tetrahydrofuran (THF). In some embodiments, the second solvent can include a solvent for dissolving the bis(arene)metal complex. In some embodiments, for example, the second solvent includes at least one of toluene, hexane, or any combination thereof.

[0041] The resulting reaction mixture can include a bis(arene) metal complex. In some embodiments, the bis(arene) metal complex is a bis(first solvent) metal complex. In some embodiments, the bis(arene) metal complex has the formula: TIFF2025529358000005.tif52170[In the formula, M is Mo, Wo or Cr; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R 3 , R 4 , R 5and R 6 two of which may be linked to form a 6-membered aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 two of which may be linked to form a six-membered aryl] This includes compounds of the formula:

[0042] In some embodiments, the bis(arene) metal complex is a bis(benzene) metal complex, a bis(toluene) metal complex, a bis(xylene) metal complex, a bis(butyltoluene) metal complex, a bis(ethylmethylbenzene) metal complex, a bis(ethylmethylbenzene) metal complex, a bis(isopropylmethylbenzene) metal complex, a bis(butylmethylbenzene) metal complex, a bis(mesitylene) metal complex, a bis(pseudocumene) metal complex, a bis(durene) metal complex, a bis(methylbenzene) metal complex, a bis(dimethylbenzene) metal complex, a bis(trimethylbenzene) metal complex, a bis(ethylbenzene) metal complex, a bis(1,4-diethylbenzene) metal complex, a bis(triethylbenzene) metal complex, a bis(propylbenzene) metal complex, a bis(butyl bis(4,4'-dimethylbiphenyl)metal complex, bis(bibenzyl)metal complex, bis(diphenylmethane)metal complex, any isomer thereof, or any combination thereof.

[0043] In some embodiments, the reaction mixture containing the bis(arene) metal complex contains no more than 50% by weight of at least one impurity, based on the total weight of the reaction mixture containing the bis(arene) metal complex. In some embodiments, the reaction mixture including the bis(arene) metal complex comprises between 0.01 wt% and 50 wt%, between 0.01 wt% and 45 wt%, between 0.01 wt% and 40 wt%, between 0.01 wt% and 35 wt%, between 0.01 wt% and 30 wt%, between 0.01 wt% and 25 wt%, between 0.01 wt% and 20 wt%, between 0.01 wt% and 15 wt%, between 0.01 wt% and 10 wt%, between 5 wt% and 50 wt%, between 10 wt% and 50 wt%, between 15 wt% and 50 wt%, between 20 wt% and 50 wt%, between 25 wt% and 50 wt%, between 30 wt% and 50 wt%, between 35 wt% and 50 wt%, between 40 wt% and 45 wt%, or between 45 wt% and 50 wt%, based on the total weight of the reaction mixture including the bis(arene) metal complex. In some embodiments, the impurities include at least one of an aluminum halide impurity, a bound aromatic impurity, a polycyclic aromatic impurity, or any combination thereof. In some embodiments, the impurities include at least one of an aluminum halide, tetrahydrofuran coordinated to an aluminum halide, a bound arene compound (e.g., a dimethylbiphenyl compound), or any combination thereof. In some embodiments, the bound arene compound has the formula: TIFF2025529358000006.tif32170[where, R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl. This includes compounds of the formula:

[0044] In some embodiments, the reaction mixture containing a bis(arene) metal complex has the formula: [MX a (Second Solvent) b ] +[MX c ] - wherein M is a metal (e.g., aluminum), X is a halide (e.g., Cl, Br, I, or F), a is 1 to 10, b is 1 to 10, and c is 1 to 10. In some embodiments, the reaction mixture containing the bis(arene) metal complex is free of compounds of the formula [AlCl(THF)] + [AlCl4] - In some embodiments, the reaction mixture containing the bis(arene) metal complex does not contain detectable levels of [AlCl2(THF)4] + [AlCl4] - Does not include.

[0045] 1 , in some embodiments, the method 100 of making a bis(arene) metal complex comprises contacting a reaction mixture comprising the bis(arene) metal complex with a separation medium to obtain a product, in some embodiments, the product comprises a purified bis(arene) metal complex and, optionally, at least one impurity, at step 106.

[0046] The reaction mixture containing the bis(arene) metal complex can be contacted with a separation medium. The contacting can include flowing the reaction mixture containing the bis(arene) metal complex through a column containing sufficient separation medium to remove at least a portion of the impurities present in the reaction mixture containing the bis(arene) metal complex. In some embodiments, prior to the contacting, the method further includes at least one of the following steps: filtering the reaction mixture containing the bis(arene) metal complex to obtain a filtered reaction mixture; drying the reaction mixture containing the bis(arene) metal complex to obtain a dried reaction mixture; contacting the reaction mixture containing the bis(arene) metal complex with an extraction solvent to obtain an extracted reaction mixture; filtering the extracted organic phase from the extracted reaction mixture; or any combination thereof. In some embodiments, the extraction solvent is an aliphatic solvent. For example, in some embodiments, the aliphatic solvent includes at least one of hexane, pentane, or any combination thereof.

[0047] The separation medium can be useful for separating (e.g., sorbing, adsorbing, absorbing, etc.) at least one impurity from a reaction mixture containing a bis(arene)metal complex. In some embodiments, the separation medium comprises at least one of neutral alumina, acidic alumina, basic alumina, florisil, silica, or any combination thereof. In some embodiments, the separation medium comprises magnesium silicate. In some embodiments, the magnesium silicate is a compound of formula MgO:XSiO2, where X is 1-10. In some embodiments, the magnesium silicate is hydrated and is a compound of formula MgO:XSiO2·H2O, where X is 1-10.

[0048] The separation medium can have an average particle size. Average particle size can refer to the average particle size of at least 50% of the separation medium. In some embodiments, the separation medium has an average particle size of 25 microns to 250 microns. In some embodiments, the separation medium has an average particle size of 25 microns to 225 microns, 25 microns to 200 microns, 25 microns to 175 microns, 25 microns to 150 microns, 25 microns to 125 microns, 25 microns to 100 microns, 25 microns to 75 microns, 25 microns to 50 microns, 50 microns to 250 microns, 75 microns to 250 microns, 100 microns to 250 microns, 125 microns to 250 microns, 150 microns to 250 microns, 175 microns to 250 microns, 200 microns to 250 microns, 225 microns to 250 microns, or any range or subrange therebetween.

[0049] Referring to FIG. 2, in some embodiments of the present disclosure, the reaction mixture containing the bis(arene) metal complex may undergo a post-synthesis aqueous extraction to obtain the resulting purified product.

[0050] In certain embodiments of the present disclosure, the post-synthesis aqueous extraction includes methods known in the relevant art. For example, one method after aqueous extraction includes drying the reaction mixture containing the bis(arene) metal complex from step 204 to obtain a dried reaction mixture; this can be partially drying the reaction mixture containing the bis(arene) metal complex to obtain a partially dried reaction mixture; contacting the dried or partially dried reaction mixture containing the bis(arene) metal complex with an extraction solvent to obtain an extracted reaction mixture; filtering the extracted organic phase from the extracted reaction mixture to obtain an organic extracted reaction filtrate; cooling the organic extracted reaction filtrate to a temperature in the range of −30 to 20° C.; contacting the organic extracted reaction filtrate with water to obtain an aqueous extracted reaction mixture; filtering the aqueous extracted reaction mixture to obtain a purified organic reaction filtrate; drying the purified organic reaction filtrate to obtain a purified product; or any combination thereof.

[0051] In some embodiments of the present disclosure, the organic extracted reaction mixture may be cooled to a range of -15 to 15°C, and in other embodiments, to a range of -10 to 10°C and any variation therebetween.

[0052] In some embodiments of the present disclosure, the extraction solvent may be an aromatic solvent. For example, in some embodiments, the aromatic solvent may include at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, m-butyltoluene, pt-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene, mesitylene, pseudocumene, durene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, iso-butylbenzene, sec-butylbenzene, t-butylbenzene, hexylbenzene, or any combination thereof.

[0053] In some embodiments of the present disclosure, the extraction solvent may be an aliphatic solvent. For example, in some embodiments, the aliphatic solvent comprises at least one of hexane, pentane, heptane, octane, cyclohexane, methylcyclohexane, or any combination thereof.

[0054] In some embodiments of the present invention, after step 204 of FIG. 2, the reaction mixture can be further purified by using a separation medium as described in this disclosure.

[0055] The product in embodiments described herein may contain a purified bis(arene) metal complex and at least one impurity that is less than the reaction mixture containing the bis(arene) metal complex (e.g., contacted with a separation medium), by weight. The product may contain 10% or less impurities. In some embodiments, for example, the product contains 9% or less impurities, 8% or less impurities, 7% or less impurities, 6% or less impurities, 5% or less impurities, 4% or less impurities, 3% or less impurities, 2% or less impurities, 1.9% or less impurities, 1.8% or less impurities, 1.7% or less impurities, 1.6% or less impurities, 1.5% or less impurities, 1.4% or less impurities, 1.3% or less impurities, 1.2% or less impurities, 1.1% or less impurities, 1% or less impurities, 0.9% or less impurities, 0.8% or less impurities, 0.7% or less impurities, 0.6% or less impurities, 0.5% or less impurities, 0.4% or less impurities, 0.3% or less impurities, 0.2% or less impurities, or 0.1% or less impurities.

[0056] In some embodiments, the product contains between 0.01% and 10% impurities, between 0.1% and 2% impurities, between 0.1% and 1.9% impurities, between 0.1% and 1.8% impurities, between 0.1% and 1.7% impurities, between 0.1% and 1.6% impurities, between 0.1% and 1.5% impurities, between 0.1% and 1.4% impurities, between 0.1% and 1.3% impurities, between 0.1% and 1.2% impurities, between 0.1% and 1% impurities, between 0.1% and 0.9% impurities, between 0.1% and 0.8% impurities, between 0.1% and 0.7% impurities, between 0.1% and 0.6% impurities, between 0.1% and 0.5% impurities, In some embodiments, the product contains between 0.1% and 0.4% impurities, between 0.1% and 0.3% impurities, between 0.2% and 2% impurities, between 0.3% and 2% impurities, between 0.4% and 2% impurities, between 0.5% and 2% impurities, between 0.6% and 2% impurities, between 0.7% and 2% impurities, between 0.8% and 2% impurities, between 0.9% and 2% impurities, between 1% and 2% impurities, between 1.1% and 2% impurities, between 1.2% and 2% impurities, between 1.3% and 2% impurities, between 1.4% and 2% impurities, between 1.5% and 2% impurities, between 1.6% and 2% impurities, between 1.7% and 2% impurities, or between 1.8% and 2% impurities. 27 Contains undetectable levels of aluminum halide as determined by Al NMR spectroscopy.

[0057] In some embodiments, the impurities include, but are not limited to, at least one of magnesium halide impurities, aryl magnesium halide impurities, aryl magnesium halide impurities coordinated by an ether solvent, anionic aryl molybdenum "ate" complexes, aluminum halide impurities, bound aromatic impurities, polycyclic aromatic impurities, or any combination thereof. In some embodiments, the impurities include at least one of aluminum halide, tetrahydrofuran coordinated to an aluminum halide, bound arene compounds (e.g., dimethylbiphenyl compounds), methylene-bridged diarene compounds, or any combination thereof. In some embodiments, the bound arene compounds have the formula: TIFF2025529358000007.tif32170[where, R 13 , R 14 , R 15, R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl. This includes compounds of the formula:

[0058] In some embodiments, the impurity is of the formula TIFF2025529358000008.tif37170[where, R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl. This includes compounds of the formula:

[0059] The presence and type of impurities, including the amount of impurities, 1 H NMR spectroscopy, 27 In some embodiments, the product may be measured using Al NMR spectroscopy, or any combination thereof. 27 Contains undetectable levels of aluminum halide as determined by Al NMR spectroscopy.

[0060] Example 1 In a two-necked round-bottom flask, add molybdenum pentachloride (MoCl5), anhydrous aluminum trichloride (AlCl3), and aluminum powder (A 0) was filled in a column packed with neutral alumina. Toluene was added, and the mixture was stirred and heated to reflux in a heat bath at approximately 110°C. After 40 hours, the mixture was cooled to approximately 40°C, and tetrahydrofuran was slowly added. The mixture was heated to reflux in a heat bath heated to approximately 100°C for approximately 15 hours, then cooled to ambient temperature and filtered to remove excess aluminum powder. The filtrate was washed with pentane and evaporated to dryness under reduced pressure (0.1 Pa). The residue was then extracted with boiling pentane, and the extract was filtered and concentrated. The solution containing the extract was passed through a column packed with neutral alumina to obtain a bis(toluene)molybdenum complex. A schematic diagram of the reaction scheme is shown in Figure 3. Figures 4A and 4B show the results after (Figure 4A) and before (Figure 4B) the solution was passed through the column. 1 4A shows the H NMR spectrum. In FIG. 4A, the broadening of the aromatic resonances is indicated by reference numeral 302. FIGS. 5A-5B show the H NMR spectrum after (FIG. 5A) and before (FIG. 5B) the solution was passed through the column. 27 5A shows the Al NMR spectrum. In FIG. 5A, the background peak of the probe is indicated by reference numeral 402.

[0061] Example 2 Bis(toluene)molybdenum synthesis with varying solvents and reaction times. A 100 mL round-bottom flask equipped with a PTFE-coated magnetic stirrer was charged with molybdenum pentachloride (3.00 g, 10.9 mmol, 1.00 equiv.), aluminum trichloride (1.66 g, 12.5 mmol, 1.15 equiv.), -325 mesh aluminum powder (0.439 g, 16.3 mmol, 1.50 equiv.), toluene (29.1 g, 316 mmol, 29 equiv.), and dodecane (18.5 g, 109 mmol, 10 equiv.). The mixture was stirred for 30 min to subside the initial exotherm (10 °C to 20 °C), then refluxed in a 135 °C oil bath for 40 h to form a biphasic reaction mixture. The reaction mixture was cooled, and the clear brownish supernatant was decanted. To the remaining dark, oily lower phase, containing the intermediate [(toluene)Mo][AlCl], toluene (29 g), magnesium powder (1.58 g, 65.3 mmol, 6.00 equiv.), and tetrahydrofuran (25.0 g) were added dropwise over approximately 10 minutes. The deep green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium-porosity fritted funnel. The solvent was removed from the green-brown filtrate under reduced pressure (100 mtorr), followed by extraction with 100 mL and 50 mL aliquots of boiling hexane to give a green solution after filtration. The filtrate was concentrated under reduced pressure to give 3.90 g of a gummy green solid. Dissolution of the green solid in a 50 / 50 mixture of toluene and hexane, followed by elution through a 3 cm high, 4.5 cm diameter bed of neutral alumina, left a reddish-brown band on the alumina, affording an emerald green solution. The green product solution was concentrated under reduced pressure to a green solid to give 1.58 g (52%) of green product, which was then sublimed in an oil bath at 110° C. and 300 mtorr to give 1.38 g (43%) of green crystalline product.

[0062] 1 H NMR (400 MHz, d-6-benzene, 298 K): δ 4.60 (br s, 5H), 1.86 (s, 3H) ppm. 13 C{ 1H}NMR (100 MHz, d-6-benzene, 289 K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.

[0063] Example 3 Bis(toluene)molybdenum synthesis with varying solvents and reaction times. A 100 mL round-bottom flask equipped with a PTFE-coated magnetic stirrer was charged with molybdenum pentachloride (3.00 g, 10.9 mmol, 1.00 equiv.), aluminum trichloride (1.66 g, 12.5 mmol, 1.15 equiv.), -325 mesh aluminum powder (0.439 g, 16.3 mmol, 1.50 equiv.), and toluene (29.1 g, 316 mmol, 29 equiv.). The mixture was stirred for 30 minutes to subside the initial exotherm (10 °C to 20 °C), then refluxed in a 135 °C oil bath for 40 hours to form a biphasic reaction mixture. The reaction mixture was allowed to cool and treated dropwise over approximately 10 minutes with magnesium powder (1.58 g, 65.3 mmol, 6.00 equiv.) and tetrahydrofuran (25.0 g). The deep green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium-porosity fritted funnel. The solvent was removed from the green-brown filtrate under reduced pressure (100 mtorr), then extracted with 100 mL and 50 mL aliquots of boiling hexane to give a green solution after filtration. The filtrate was concentrated under reduced pressure to give 3.30 g of a gummy green solid. The green solid was dissolved in a 50 / 50 mixture of toluene and hexane and eluted through a 3 cm high, 4.5 cm diameter bed of neutral alumina, leaving a reddish-brown band on the alumina, giving an emerald green solution. The green product solution was concentrated under reduced pressure to a green solid to give 2.00 g (52%) of green product. The solid green product was then sublimed in an oil bath at 110 °C and 300 mtorr to give 1.38 g (43%) of green crystalline product. See NMR data: 1 H NMR (400 MHz, d-6-benzene, 298 K): δ 4.60 (br s, 5H), 1.86 (s, 3H) ppm. 13 C{ 1H}NMR (100 MHz, d-6-benzene, 289 K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.

[0064] Example 4 Bis(toluene)molybdenum synthesis with varying solvents and reaction times. The same procedure as in Example 2 was carried out, except that the initial reflux time for the reaction step to form [(toluene)Mo][AlCl] was 4 hours instead of 40 hours.

[0065] Examples 2 to 4 relate to the synthesis of bis(toluene)molybdenum. In each of Examples 2 to 4, the solvent and reaction time were varied. Table 1 below summarizes the solvents and reaction times used in each of Examples 2 to 4. TIFF2025529358000009.tif48170

[0066] 5A-5C show stacked views of crude products from Example 2 (FIG. 5A), Example 3 (FIG. 5B), and Example 4 (FIG. 5C), according to some embodiments. 1 The H NMR spectrum is shown in Figure 5C. In Figure 5C, 502 corresponds to the aromatic resonance from the product bound to toluene, and 504 corresponds to the resonance from the impurity coordinated to tetrahydrofuran. When shorter reflux times were used, the relative amount of impurity present was much higher in the spectrum corresponding to Example 4. Furthermore, the peak width of the aromatic resonance corresponding to the bis(toluene)molybdenum product was understood to be related to the presence of an impurity consisting of molybdenum bound to other aromatic impurities or other impurities present that may function as Lewis base-type ligands. From these spectra, 1 It can be seen that the crude product with the fewest impurities observed by H NMR is that from Example 3. From these results it is clear that when reduction of [(toluene)Mo][AlCl] was carried out using aluminum instead of magnesium, elution from alumina media resulted in the removal of many other impurities besides the tetrachloroaluminate present.

[0067] Example 5 Synthesis of bis(toluene)molybdenum on a 10 g scale by heat / vacuum treatment of the hexane extract. A 250 mL round-bottom flask equipped with a PTFE-coated magnetic stirring egg was charged with molybdenum pentachloride (10.00 g, 36.6 mmol, 1.00 equiv.), aluminum trichloride (5.59 g, 42.0 mmol, 1.15 equiv.), -325 mesh aluminum powder (1.48 g, 54.9 mmol, 1.50 equiv.), and toluene (101 g, 1.10 mmol, 30 equiv.). The mixture was stirred for 1 h to subside the initial exotherm (15 °C to 20 °C) and then refluxed in a 135 °C oil bath for 40 h to form a biphasic reaction mixture. The reaction mixture was allowed to cool and treated dropwise over approximately 15 min with magnesium powder (5.32 g, 219 mmol, 6.00 equiv.) and tetrahydrofuran (84 g). The dark green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium-porosity fritted funnel. The solvent was removed from the green-brown filtrate under reduced pressure (100 mtorr), extracted with two 250 mL aliquots of boiling hexane, filtered hot on a medium-porosity frit, and then the solvent was removed under reduced pressure. This revealed the presence of an impurity with resonances corresponding to coordinated tetrahydrofuran (δ 3.89 (br s, 2H), 1.35 (br s, 2H) ppm). 1 The stripped hexane extract was analyzed by H NMR. The material was then heated in a 100°C oil bath under 100 mtorr vacuum for a total of 3.5 hours. The hexane extraction process was repeated, followed by stripping under reduced pressure, yielding 12.07 g of a sticky green residue. The 1H NMR showed a loss of resonance due to the impurity of coordinated tetrahydrofuran. 1 The residue was analyzed by H NMR and also by TGA, which showed that approximately 46 wt. % of the material (5.6 g) corresponded to the bis(toluene)molybdenum product. This residue was purified by vacuum sublimation in an oil bath at 115°C-140°C at 100 mtorr pressure to give two sublimate fractions: 3.77 g and 2.17 g of the expected bis(toluene)molybdenum product (60% overall yield). TGA analysis of the two fractions showed 6.3 and 7.0% residue, respectively.

[0068] Using magnesium as a reducing agent for the intermediate [(toluene)2Mo][AlCl4], good yields were achieved, and purification by sublimation from the magnesium-reduced product was achieved without sacrificing yield.

[0069] Example 6 Synthesis of bis(toluene)molybdenum using aluminum and magnesium as successive reducing agents. A 100 mL round-bottom flask equipped with a PTFE-coated magnetic stirring egg was charged with molybdenum pentachloride (3.00 g, 10.9 mmol, 1.00 equiv.), aluminum trichloride (1.66 g, 12.5 mmol, 1.15 equiv.), -325 mesh aluminum powder (1.17, 43.6 mmol, 4.00 equiv.), and toluene (30.1 g, 327 mmol, 30 equiv.). The mixture was stirred for 1 hour to subside the initial exotherm (15°C to 20°C) and then refluxed in a 135°C oil bath for 40 hours to form a biphasic reaction mixture. The reaction mixture was allowed to cool and then treated with tetrahydrofuran (25.0 g) in a dropwise manner over approximately 15 minutes. The dark green reaction mixture was heated to reflux for 18 hours, a small aliquot was removed, and the solvent was removed. 1 H NMR and 27 This material was analyzed by Al NMR. 1 The 1 H NMR spectrum showed resonances corresponding to the methyl groups of the toluene ligand and tetrahydrofuran resonances corresponding to [AlCl2(THF)4][AlCl4], but no aromatic protons of toluene were observed. 27The Al NMR spectrum showed a resonance at 104.0 ppm corresponding to the impurity [AlCl2(THF)4][AlCl4]. The reaction mixture was then treated with magnesium powder (1.58 g, 65.3 mmol, 6.00 equiv.), refluxed for an additional 18 h, filtered through a medium-porosity fritted funnel, and the volatiles removed under reduced pressure. The solvent was removed from the green-brown filtrate under reduced pressure (100 mtorr), heated at 100°C for 15 min under reduced pressure, and then extracted with 100 mL and 50 mL aliquots of boiling hexane to give a green solution after filtration. Removal of the solvent from the green solution gave 3.24 g of a sticky green solid, indicating the formation of the desired product in the absence of the impurity [AlCl2(THF)4][AlCl4]. 1 H NMR and 27 The green solid was analyzed by Al NMR. 1 H NMR (400MHz, d-6-benzene, 298K): δ4.63(d,2H), 4.59(t,2H), 4.51(t,1H) 1.86(s,3H)ppm. 13 C{ 1 H}NMR (100 MHz, d-6-benzene, 289 K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.

[0070] 6A-6B show the results of the crude product after aluminum reduction (FIG. 6A) and after sequential magnesium reduction (FIG. 6B), according to some embodiments. 1 7A-7B show H NMR spectra of the crude product after aluminum reduction (FIG. 7A) and after sequential magnesium reduction (FIG. 7B), according to some embodiments. 27 Al NMR is shown.

[0071] Example 7 Synthesis and split-batch purification of bis(toluene)molybdenum on a 36 g scale using aluminum as the reducing agent. A three-neck, 1 L round-bottom flask was charged with molybdenum pentachloride (36.0 g, 131 mmol, 1.00 equiv.), aluminum trichloride (19.9 g, 150 mmol, 1.15 equiv.), -325 mesh aluminum powder (14.1 g, 524 mmol, 4.00 equiv.), and toluene (350 g, 3.80 mol, 29 equiv.). The flask was equipped with a mechanical stirrer (glass stir shaft, PTFE stir bearing, PTFE stirring paddle) and stirred at approximately 250 RPM. The mixture was stirred for approximately 30 minutes to quench the initial exotherm (5 °C to 10 °C), then refluxed in a 135 °C oil bath for 40 hours to form a biphasic reaction mixture. The reaction mixture was allowed to cool and then slowly treated with tetrahydrofuran (302 g) over approximately 2 hours. The reaction mixture was then refluxed for 18 hours, allowed to cool, and filtered through a medium-porosity fritted funnel. The solvent was removed from the green-brown filtrate under reduced pressure (100 mtorr), extracted with two 250 mL aliquots of boiling hexane, filtered hot on a medium-porosity frit, and then the solvent was removed under reduced pressure to give 114 g of crude material. This crude product was extracted with boiling pentane (500 mL, 4x, 2 L total) and filtered to give a green solution. Evaporation of the solvent from this solution under reduced pressure gave 20.10 g (55% crude yield extracted with pentane) of a green solid. In addition to the product, the presence of the [AlCl2(THF)4][AlCl4] impurity was noted. 1 H NMR and 27 The green solid was analyzed by Al NMR. The crude product extracted with pentane was then divided into six approximately equal mass portions and purified according to the method shown in Table 2 below. As shown in Table 2, passing the bis(arene)molybdenum complex through an adsorption medium was superior to recrystallization, at least in terms of purity and yield of the isolated product. Sublimation of the impure product was also observed to result in lower yield and lower purity. TIFF2025529358000010.tif92170

[0072] Example 8 Independent synthesis of [AlCl2(THF)4][AlCl4]. 1.0 g of AlCl3 (7.50 mmol, 1 equiv.) was weighed into a clear 40 ml scintillation vial containing a microstir bar. 10 ml of toluene was added to the vial, and the mixture was stirred to dissolve the solid. The reaction mixture was heated and stirred while 1.1 g (15.0 mmol, 2 equiv.) of THF was added dropwise. The reaction mixture was heated at 100°C for 2 hours, and the solvent was slowly evaporated to give a colorless crystalline solid, which was analyzed by NMR and shown to be consistent with the major aluminum species produced as an impurity in the bis(toluene)molybdenum synthesis. See NMR data: 1 H NMR (400MHz, d-6-benzene, 298K): δ3.58(s,2H), 0.88(s,2H)ppm. 13 C{ 1 H}NMR (100 MHz, d-6-benzene, 289 K): δ 74.39, 24.67 ppm. 27 Al NMR (104 MHz, d-6-benzene, 289 K): δ 104.0 ppm.

[0073] Example 9 Synthesis of bis(toluene)molybdenum from MoCl5 on a 50 g scale. A 3 L round-bottom flask was charged with molybdenum pentachloride (50.548 g, 185 mmol, 1.0 equiv.), aluminum trichloride (56.176 g, 421 mmol, 2.28 equiv.), and aluminum powder (7.395 g, 274 mmol, 1.48 equiv.). Toluene (505 g, 5.48 mol, 29.6 equiv.) was charged to the flask, and the reaction mixture was stirred at ambient temperature for 1 hour. The reaction mixture was stirred and heated to reflux for 24 hours. The reaction mixture was cooled, then chilled in an ice bath and charged dropwise with magnesium powder (31.13 g, 1.28 mol, 6.91 equiv.) and tetrahydrofuran (422 g), ensuring the internal temperature did not exceed 25 °C. The reaction was heated to reflux (approximately 86°C) for 18 hours and then cooled to ambient temperature. The reaction mixture was filtered into a 2 L round-bottom flask, and residual salts were washed with 300 mL of anhydrous toluene. The solvent was removed from the combined filtrate under reduced pressure to yield a dark green to brown solid. The crude solid was extracted twice with hot (50°C) anhydrous hexanes (1224 g aliquot and 578 g aliquot), with successive filtration after each hot extraction to yield a clear green product solution in the hexanes. The solvent was removed from the combined filtrate from the hot hexanes washes to yield 50.2 g of product. The hexanes-extracted product was dissolved in a solution of 300 mL of toluene and 200 ml of hexanes, cooled to approximately 5°C in an ice bath, and treated dropwise with 60 mL of degassed, deionized water. This resulted in the formation of a light precipitate that was removed by filtration using a medium-porosity filter funnel. The toluene was then removed from the purified filtrate under reduced pressure to yield 50.2 g of product. 1 27.3 g of a green solid was obtained that was 92% pure by H NMR (quantitative vs. hexamethyldisiloxane internal standard). TGA analysis of the product indicated a purity of 88% based on the residual mass. 1 The yield of the reaction based on 1 H NMR weighted purity was 49%.

[0074] Example 10 MoCl on a 50 g scale according to the reaction scheme in Figure 9 4 Synthesis of bis(toluene)molybdenum from toluene.A 2 L reaction flask was charged with MoCl (50.0 g, 210 mmol, 1.00 equiv.), aluminum chloride (50.3 g, 378 mmol, 1.80 equiv.), aluminum powder (6.50 g, 241 mmol, 1.15 equiv.), and toluene (580 g, 6.3 mol, 30.0 equiv.). The reaction mixture was stirred and heated to reflux in a 135° C. oil bath for 41 hours. The reaction mixture was cooled, then chilled in an ice bath and charged dropwise with magnesium powder (28.0 g, 1.155 mol, 5.50 equiv.) and tetrahydrofuran (484 g, 6.72 mol, 32.0 equiv.). The reaction was heated to reflux (approximately 86° C.) for 8 hours. It was then cooled and allowed to stand for approximately 72 hours. The reaction mixture was then evaporated to near dryness under reduced pressure. The resulting green solid was then dissolved in approximately 500 mL of anhydrous toluene and filtered through a medium porosity fritted funnel to give a green solution. The toluene was then removed from the filtrate under reduced pressure to give 49% and 50% purity, respectively. 1 79.36 g of a sticky green solid was obtained, which was analyzed for purity by H NMR (quantitative vs. hexamethyldisiloxane internal standard) and TGA. The sticky green solid was dissolved in approximately 400 mL of toluene, cooled to approximately 5° C. in an ice bath, and then treated with 20 mL of degassed, deionized water for 45 minutes with vigorous stirring so that the internal temperature did not exceed 20° C. This resulted in the formation of a light precipitate that was removed by filtration using a medium porosity filter funnel. The toluene was then removed from the purified filtrate under reduced pressure to afford a soluble solid. 1 47.31 g of a green solid was obtained that was 85% pure by H NMR. The green solid was transferred to a sublimation apparatus and further purified by sublimation (120-140 °C, 100 mtorr), as shown in Figure 10. 1 36.3 g of bis(toluene)molybdenum was obtained with a purity of 94% by 1 H NMR and 97% by TGA.

[0075] Example 11 According to the reaction scheme in Figure 9Synthesis of bis(toluene)molybdenum from molybdenum tetrachloride on a 10 g scale. A 500 mL three-neck round-bottom flask was charged with molybdenum tetrachloride (10 g, 42.0 mmol, 1.0 equiv.), aluminum trichloride (9.99 g, 75.0 mmol, 1.79 equiv.), aluminum powder (1.30 g, 48.3 mmol, 1.15 equiv.), and toluene (116 g, 1260 mmol, 30.0 equiv.). The reaction mixture was stirred and heated to reflux for 44 hours. The reaction mixture was cooled, then chilled in an ice bath and charged dropwise with magnesium powder (5.61 g, 231 mol, 5.50 equiv.) and approximately 100 mL of anhydrous tetrahydrofuran, maintaining the internal temperature below 20°C. The reaction was heated to reflux (approximately 87°C) for 17 hours and then cooled to ambient temperature. The solvent was then distilled off under reduced pressure until the mixture reached a nearly dry state. The crude product was then extracted with 400 mL of toluene and filtered through a medium-porosity frit into a 1 L flask. Residual salts were washed off with four 100 mL aliquots of toluene and successively filtered to obtain approximately 800 mL of a green product solution. The green product solution was cooled in an ice bath, vigorously stirred, and treated dropwise with 15 mL of degassed, deionized water over a period of 1 hour. The mixture was treated with approximately 5 g of anhydrous magnesium sulfate and then filtered to remove the precipitate. The solvent was removed from the filtrate under reduced pressure to obtain approximately 800 mL of a green product solution. 1 Obtained 11.15 g of bis(toluene)molybdenum (78% yield) with a purity of 82% by H NMR. TGA analysis of the product showed a total residue of 6%, of which 85% was volatile residue, attributed to bis(toluene)molybdenum weight transitions, as shown in Figure 11.

[0076] Aspects Various embodiments are described below. It should be understood that any one or more of the features described in the following embodiments can be combined with any one or more of the other embodiments.

[0077] Aspect 1. 1. A method comprising: contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture comprising an intermediate complex; contacting the intermediate complex with a second metal component in a reaction mixture comprising a second solvent to form a reaction mixture comprising a bis(arene) metal complex; and Obtaining the product Including, The method, wherein the product comprises a purified bis(arene) metal complex having less than 10% impurities.

[0078] Embodiment 2. The method of embodiment 1, wherein obtaining the product comprises subjecting the reaction mixture to a post-synthesis aqueous extraction.

[0079] Aspect 3. A method comprising: contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture comprising an intermediate complex; contacting the intermediate complex with a second metal component in a reaction mixture comprising a second solvent to form a reaction mixture comprising a bis(arene) metal complex; and contacting a reaction mixture containing a bis(arene) metal complex with a separation medium to obtain a product. Including, The method, wherein the product comprises a purified bis(arene) metal complex and less than 10% impurities.

[0080] Embodiment 4. The method of any one of embodiments 1 to 3, wherein the contacting of the metal halide proceeds at a temperature of at least 50°C to 200°C.

[0081] Embodiment 5. The method of any one of embodiments 1-4, wherein the metal halide comprises at least one of MoCl2, MoCl3, MoCl4, MoCl5, MoCl6, CrCl2, CrCl3, WCl2, WCl3, WCl4, WCl5, WCl6, or any combination thereof.

[0082] Embodiment 6. The method of any one of embodiments 1-5, wherein the first metal component comprises at least one of Li, Na, K, Rb, Cs, Mg, Ca, Cd, Sr, Ba, Al, Ga, In, Zn, Sn, or any combination thereof.

[0083] Embodiment 7. The method of any one of embodiments 1-6, wherein the aluminum halide comprises at least one of aluminum chloride, aluminum bromide, aluminum iodide, or any combination thereof.

[0084] Embodiment 8. The first solvent has the formula: TIFF2025529358000011.tif36170[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 two of which may be linked to form a six-membered aryl] including the compound The method according to any one of aspects 1 to 7.

[0085] Aspect 9. The first solvent has the formula: TIFF2025529358000012.tif32170[in the formula, R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11and R 12 two of which may be linked to form a six-membered aryl] including the compound The method according to any one of aspects 1 to 7.

[0086] Aspect 10. The method of any one of aspects 1-9, wherein the first solvent is an aromatic solvent comprising at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, m-t-butyltoluene, pt-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene, mesitylene, pseudocumene, durene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, iso-butylbenzene, sec-butylbenzene, t-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenylene, dimethylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomer thereof, or any combination thereof.

[0087] Aspect 11. An intermediate complex having the formula: [Bis(first solvent)metal] + [Aluminum halide] - , wherein the metal is Mo, Cr or W; wherein the halide is Cl, Br, or I. is a complex of The method according to any one of aspects 1 to 10.

[0088] Embodiment 12. The method of any one of embodiments 1 to 11, wherein the contacting of the intermediate complex proceeds at a temperature between 0°C and 150°C.

[0089] Embodiment 13. The method of any one of embodiments 1-12, wherein the second metal component comprises at least one of Li, Na, K, Rb, Cs, Mg, Ca, Cd, Sr, Ba, Al, Ga, In, Zn, Sn, or any combination thereof.

[0090] Embodiment 14. The method of any one of embodiments 1-13, wherein the second solvent is an ether solvent comprising at least one of tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane (DME), triglyme, diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, methyl tert-butyl ether (MTBE), or any combination thereof.

[0091] Aspect 15. A bis(arene) metal complex having the formula: TIFF2025529358000013.tif52170 (in the formula, M is Mo, Wo or Cr; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 two of which may be linked to form a 6-membered aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12two of which may be linked to form a six-membered aryl] including the compound A method according to any one of aspects 1 to 14.

[0092] Aspect 16. The bis(arene) metal complex is one of the following: a bis(benzene) metal complex, a bis(toluene) metal complex, a bis(xylene) metal complex, a bis(butyltoluene) metal complex, a bis(ethylmethylbenzene) metal complex, a bis(ethylmethylbenzene) metal complex, a bis(isopropylmethylbenzene) metal complex, a bis(butylmethylbenzene) metal complex, a bis(mesitylene) metal complex, a bis(pseudocumene) metal complex, a bis(durene) metal complex, a bis(methylbenzene) metal complex, a bis(dimethylbenzene) metal complex, a bis(trimethylbenzene) metal complex, a bis(ethylbenzene) metal complex, a bis(1,4-diethylbenzene) metal complex, a bis(triethylbenzene) metal complex, a bis(propylbenzene) metal complex, or a bis(butylbenzene) metal complex. , a bis(iso-butylbenzene) metal complex, a bis(sec-butylbenzene) metal complex, a bis(t-butylbenzene) metal complex, a bis(hexylbenzene) metal complex, a bis(styrene) metal complex, a bis(naphthalene) metal complex, a bis(anthracene) metal complex, a bis(phenanthrene) metal complex, a bis(biphenyl) metal complex, a bis(terphenyl) metal complex, a bis(methylnaphthalene) metal complex, a bis(biphenylene) metal complex, a bis(dimethylnaphthalene) metal complex, a bis(methylanthracene) metal complex, a bis(4,4'-dimethylbiphenyl) metal complex, a bis(bibenzyl) metal complex, a bis(diphenylmethane) metal complex, any isomer thereof, or any combination thereof.

[0093] Embodiment 17. The method of any one of embodiments 1 to 16, wherein the separation medium comprises at least one of neutral alumina, acidic alumina, basic alumina, magnesium silicate, silica, or any combination thereof.

[0094] Embodiment 18. The method of any one of embodiments 1 to 17, wherein the product contains 1% to 2% impurities.

[0095] Embodiment 19. The method of any one of embodiments 1 to 18, wherein the product contains between 0.01% and 2% impurities.

[0096] Embodiment 20. The method of any one of embodiments 1 to 19, wherein the impurity comprises at least one of an aluminum halide, tetrahydrofuran coordinated to an aluminum halide, a bound arene compound, or any combination thereof.

[0097] Aspect 21. The linked arene compound has the formula: TIFF2025529358000014.tif32170[In the formula, R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl. 21. The method of embodiment 20, comprising the compound of formula:

[0098] Aspect 22. The product is: 27 Aspect 21. The method of any one of aspects 1-20, comprising undetectable levels of aluminum halide as determined by Al NMR spectroscopy.

[0099] Embodiment 23. A method of synthesis comprising: contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture comprising an intermediate complex; and contacting the intermediate complex with a second metal component in a reaction mixture comprising a second solvent to form a reaction mixture comprising a bis(arene) metal complex; A method comprising:

[0100] Embodiment 24. The method of embodiment 23, wherein the metal halide comprises at least one of MoCl2, MoCl3, MoCl4, MoCl5, MoCl6, CrCl2, CrCl3, WCl2, WCl3, WCl4, WCl5, WCl6, or any combination thereof.

[0101] Embodiment 25. The method of any one of embodiments 23-24, wherein the first metal component comprises at least one of Li, Na, K, Rb, Cs, Mg, Ca, Cd, Sr, Ba, Al, Ga, In, Zn, Sn, or any combination thereof.

[0102] Embodiment 26 The method of any one of embodiments 23 to 25, wherein the aluminum halide comprises at least one of aluminum chloride, aluminum bromide, aluminum iodide, or any combination thereof.

[0103] Embodiment 27. The first solvent has the formula: TIFF2025529358000015.tif36170[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; or R 1 , R 2 , R 3 , R 4 , R 5 and R 6 two of which may be linked to form a six-membered aryl] a compound of, or formula: TIFF2025529358000016.tif32170[in the formula, R 7 , R 8 , R 9 , R 10 , R 11 and R 12are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 two of which may be linked to form a six-membered aryl] 27. The method of any one of aspects 23-26, comprising a compound of the formula:

[0104] Embodiment 28. The intermediate complex has the formula: [Bis(first solvent)metal] + [Aluminum halide] - , wherein the metal is Mo, Cr or W; wherein the halide is Cl, Br, or I. 28. The method of any one of aspects 23 to 27, wherein the compound is a complex of

[0105] Embodiment 29. The method of any one of embodiments 23 to 28, wherein the second metal component comprises at least one of Li, Na, K, Rb, Cs, Mg, Ca, Cd, Sr, Ba, Al, Ga, In, Zn, Sn, or any combination thereof.

[0106] Embodiment 30. The method of any one of embodiments 23 to 29, wherein the second solvent is an ether solvent comprising at least one of tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane (DME), triglyme, diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, methyl tert-butyl ether (MTBE), or any combination thereof.

[0107] Aspect 31. A bis(arene) metal complex having the formula: TIFF2025529358000017.tif52170[In the formula, M is Mo, Wo or Cr; R 1 , R 2 , R3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 two of which may be linked to form a 6-membered aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 two of which may be linked to form a six-membered aryl] 31. The method of any one of aspects 23 to 30, comprising a compound of the formula:

[0108] 32. A reaction mixture containing a bis(arene) metal complex contains detectable levels of [AlCl2(THF)4] + [AlCl4] - 32. The method of any one of aspects 23 to 31, wherein the method does not include:

[0109] Embodiment 33. A method of purification, comprising: obtaining a reaction mixture comprising a bis(arene) metal complex and at least one impurity; and contacting a reaction mixture containing a bis(arene) metal complex with a separation medium to obtain a product. Including, The product comprises a purified bis(arene) metal complex; The method wherein the product contains less, by weight, of at least one impurity than the reaction mixture containing the bis(arene) metal complex.

[0110] Aspect 34. The bis(arene) metal complex has the formula: TIFF2025529358000018.tif52170[In the formula, M is Mo, Wo or Cr; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 two of which may be linked to form a 6-membered aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 two of which may be linked to form a six-membered aryl] 34. The method of embodiment 33, comprising the compound of formula:

[0111] Embodiment 35. The method of any one of embodiments 33-34, wherein the at least one impurity comprises at least one of a metal halide, an arene coordinated to a metal halide, a metal halide complex, or any combination thereof.

[0112] Embodiment 36. The method of any one of embodiments 33-35, wherein the at least one impurity comprises at least one of an aluminum halide, tetrahydrofuran coordinated to an aluminum halide, an aluminum halide complex, a bound arene compound, or any combination thereof.

[0113] 37. A reaction mixture containing a bis(arene) metal complex contains detectable levels of [AlCl2(THF)4] + [AlCl4] - 37. The method of any one of aspects 33 to 36, wherein the method does not include:

[0114] Embodiment 38 The method of any one of embodiments 33 to 37, wherein the reaction mixture containing the bis(arene) metal complex comprises a solvent for dissolving the bis(arene) metal complex.

[0115] Embodiment 39 The method of any one of embodiments 33 to 38, wherein the reaction mixture comprising the bis(arene)metal complex comprises at least one of toluene, hexane, or any combination thereof.

[0116] Embodiment 40. The method of any one of embodiments 33 to 39, wherein the separation medium comprises at least one of neutral alumina, acidic alumina, basic alumina, magnesium silicate, silica, or any combination thereof.

[0117] Embodiment 41 The method of any one of embodiments 33 to 40, wherein the product has 10 wt% or less of at least one impurity, based on the total weight of the product.

[0118] Embodiment 42. The method of any one of embodiments 33 to 41, wherein the product has 2 wt.% or less of at least one impurity, based on the total weight of the product.

[0119] Aspect 43. A compound of the formula: TIFF2025529358000019.tif52170[In the formula, M is Mo, Wo or Cr; R1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 two of which may be linked to form a 6-membered aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 two of which may be linked to form a six-membered aryl] A composition comprising a bis(arene) metal complex of

[0120] Embodiment 44. The composition of embodiment 43, wherein the bis(arene) metal complex contains less than 10% impurities.

[0121] Embodiment 45. The composition of any one of embodiments 43-44, wherein the bis(arene) metal complex contains less than 5% impurities.

[0122] Embodiment 46. The composition of any one of embodiments 43-45, wherein the bis(arene) metal complex contains less than 1% impurities.

[0123] Embodiment 47. The composition of embodiments 43-46, wherein the impurity comprises at least one of an aluminum halide, tetrahydrofuran coordinated to an aluminum halide, a linked arene compound, a methylene-bridged arene, or any combination thereof.

[0124] 48. The impurity is the following compound: TIFF2025529358000020.tif73170[where, R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; magnesium halides, aluminum halides, alkali metal halides, alkaline earth metal halides, aryl magnesium halides, aryl aluminum, aryl aluminum halides, aluminum halide tetrahydrofuran complexes, aryl magnesium halide tetrahydrofuran complexes, metal halide compounds, anionic aryl metal complexes with alkali metal cations, anionic aryl metal complexes with alkaline earth metal cations, compounds of the formula: TIFF2025529358000021.tif113170 (in the formula, M is Mo, Wo or Cr; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R 1 , R 2 , R3 , R 4 , R 5 and R 6 two of which may be linked to form a 6-membered aryl; During the ceremony, R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl During the ceremony, R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl. an oligomeric metal compound consisting of a metal coordinated by a compound of 48. The composition of any one of aspects 43 to 47, comprising at least one of:

[0125] It should be understood that changes may be made in details, particularly in matters of the materials of construction used and the shape, size and arrangement of parts without departing from the scope of the present disclosure. The specification and described embodiments are examples, the true scope and spirit of the present disclosure being indicated by the appended claims.

Claims

1. 1. A method comprising: contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction mixture comprising an intermediate complex; contacting the intermediate complex with a second metal component in a reaction mixture comprising a second solvent to form a reaction mixture comprising a bis(arene)metal complex; and Obtaining the product Including, The method wherein the product comprises a purified bis(arene)metal complex having less than 10% impurities.

2. 10. The method of claim 1, wherein the contacting of the metal halide proceeds at a temperature of at least 50°C to 200°C.

3. The metal halide is MoCl ２ , MoCl ３ , MoCl ４ , MoCl ５ , MoCl ６ , CrCl ２ , CrCl ３ , WCl ２ , WCl ３ , WCl ４ , WCl ５ , WCl ６ or any combination thereof.

4. 10. The method of claim 1, wherein the first metal component comprises at least one of Li, Na, K, Rb, Cs, Mg, Ca, Cd, Sr, Ba, Al, Ga, In, Zn, Sn, or any combination thereof.

5. 10. The method of claim 1, wherein the aluminum halide comprises at least one of aluminum chloride, aluminum bromide, aluminum iodide, or any combination thereof.

6. The first solvent has the formula: [In the formula, R １ , R ２ , R ３ , R ４ , R ５ and R ６ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R １ , R ２ , R ３ , R ４ , R ５ and R ６ two of which may be linked to form a six-membered aryl.

10. The method of claim 1, comprising the compound of formula:

7. The first solvent has the formula: [In the formula, R ７ , R ８ , R ９ , R １０ , R １１ and R １２ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R ７ , R ８ , R ９ , R １０ , R １１ and R １２ two of which may form a six-membered aryl.

10. The method of claim 1, comprising the compound of formula:

8. 2. The method of claim 1, wherein the first solvent is an aromatic solvent comprising at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, o-t-butyltoluene, m-t-butyltoluene, p-t-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene, mesitylene, pseudocumene, durene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, iso-butylbenzene, sec-butylbenzene, t-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenylene, dimethylnaphthalene, methylanthracene, 4,4′-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomer thereof, or any combination thereof.

9. The intermediate complex has the formula: [Bis(first solvent)metal] ＋ [Aluminum halide] － , wherein the metal is Mo, Cr or W; wherein the halide is Cl, Br or I. The method of claim 1, wherein the compound is a complex of

10. 10. The method of claim 1, wherein obtaining the product comprises subjecting the reaction mixture to a post-synthesis aqueous extraction.

11. 11. The method of claim 10, wherein the product is further purified by using a separation medium.

12. 10. The method of claim 1, wherein obtaining the product comprises contacting a reaction mixture containing the bis(arene) metal complex with a separation medium.

13. The bis(arene) metal complex has the formula: [In the formula, M is Mo, Wo or Cr; R １ , R ２ , R ３ , R ４ , R ５ and R ６ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R １ , R ２ , R ３ , R ４ , R ５ and R ６ two of which may be linked to form a 6-membered aryl; R ７ , R ８ , R ９ , R １０ , R １１ and R １２ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R ７ , R ８ , R ９ , R １０ , R １１ and R １２ two of which may be linked to form a six-membered aryl.

10. The method of claim 1, comprising the compound of formula:

14. The bis(arene) metal complexes include the following: bis(benzene) metal complexes, bis(toluene) metal complexes, bis(xylene) metal complexes, bis(butyltoluene) metal complexes, bis(ethylmethylbenzene) metal complexes, bis(ethylmethylbenzene) metal complexes, bis(isopropylmethylbenzene) metal complexes, bis(butylmethylbenzene) metal complexes, bis(mesitylene) metal complexes, bis(pseudocumene) metal complexes, bis(durene) metal complexes, bis(methylbenzene) metal complexes, bis(dimethylbenzene) metal complexes, bis(trimethylbenzene) metal complexes, bis(ethylbenzene) metal complexes, bis(1,4-diethylbenzene) metal complexes, bis(triethylbenzene) metal complexes, bis(propylbenzene) metal complexes, and bis(butylbenzene) metal complexes.

10. The method of claim 1, wherein the metal complex comprises at least one of a bis(isobutylbenzene) metal complex, a bis(sec-butylbenzene) metal complex, a bis(t-butylbenzene) metal complex, a bis(hexylbenzene) metal complex, a bis(styrene) metal complex, a bis(naphthalene) metal complex, a bis(anthracene) metal complex, a bis(phenanthrene) metal complex, a bis(biphenyl) metal complex, a bis(terphenyl) metal complex, a bis(methylnaphthalene) metal complex, a bis(biphenylene) metal complex, a bis(dimethylnaphthalene) metal complex, a bis(methylanthracene) metal complex, a bis(4,4'-dimethylbiphenyl) metal complex, a bis(bibenzyl) metal complex, a bis(diphenylmethane) metal complex, any isomer thereof, or any combination thereof.

15. The following formula: [In the formula, M is Mo, Wo or Cr; R １ , R ２ , R ３ , R ４ , R ５ and R ６ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R １ , R ２ , R ３ , R ４ , R ５ and R ６ two of may be linked to form a 6-membered aryl; R ７ , R ８ , R ９ , R １０ , R １１ and R １２ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R ７ , R ８ , R ９ , R １０ , R １１ and R １２ two of which may be linked to form a six-membered aryl. A composition comprising a bis(arene) metal complex of

16. 16. The composition of claim 15, wherein the bis(arene) metal complex contains less than 10% impurities.

17. 16. The composition of claim 15, wherein the bis(arene) metal complex contains less than 5% impurities.

18. 16. The composition of claim 15, wherein the bis(arene) metal complex contains less than 1% impurities.

19. 17. The composition of claim 16, wherein the impurities comprise at least one of an aluminum halide, tetrahydrofuran coordinated to an aluminum halide, a linked arene compound, a methylene-bridged arene, or any combination thereof.

20. The impurity may be the following compound: [In the formula, R １３ , R １４ , R １５ , R １６ , R １７ , R １８ , R １９ , R ２０ , R ２１ and R ２２ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R ２３ , R ２４ , R ２５ , R ２６ , R ２７ , R ２８ , R ２９ , R ３０ , R ３１ , R ３２ , R ３３ and R ３４ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; magnesium halides, aluminum halides, alkali metal halides, alkaline earth metal halides, aryl magnesium halides, aryl aluminum, aryl aluminum halides, aluminum halide tetrahydrofuran complexes, aryl magnesium halide tetrahydrofuran complexes, metal halide compounds, anionic aryl metal complexes with alkali metal cations, anionic aryl metal complexes with alkaline earth metal cations, compounds of the formula: (In the formula, M is Mo, Wo or Cr; R １ , R ２ , R ３ , R ４ , R ５ and R ６ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; R １ , R ２ , R ３ , R ４ , R ５ and R ６ two of which may be linked to form a 6-membered aryl; During the ceremony, R １３ , R １４ , R １５ , R １６ , R １７ , R １８ , R １９ , R ２０ , R ２１ and R ２２ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl; During the ceremony, R ２３ , R ２４ , R ２５ , R ２６ , R ２７ , R ２８ , R ２９ , R ３０ , R ３１ , R ３２ , R ３３ and R ３４ are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, or aryl. an oligomeric metal compound consisting of a metal coordinated by a compound of the formula The composition of claim 16, comprising at least one of:

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