Bis (arene) metal complexes and related methods

Abstract

The present invention provides methods relating to the preparation and purification of bis (arene) metal complexes. A method can include contacting a metal halide with a first metal component and an aluminum halide in a first solvent, thereby forming a reaction mixture including an intermediate complex. A method can include 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. A process can include contacting a reaction mixture comprising the bis (arene) metal complex with a separation medium, thereby obtaining a product. Bis (arene) metal complexes are also provided.

Description

Technical Field

[0001] The present disclosure relates to the synthesis and purification of bis(arene)metal complexes and related compositions and methods. Background Art

[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 are not easy to separate and purify. Organometallic compounds are also often produced in low yields. This poses problems in scaling up the process for commercial production. Summary of the invention

[0003] Some embodiments of the present disclosure are directed to a method. In some embodiments, the method comprises 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 obtaining a product.

[0004] Some embodiments of the present disclosure relate to a method. In some embodiments, the method comprises 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(aromatic) metal complex; and contacting the reaction mixture comprising the bis(aromatic) metal complex with a separation medium to obtain a product. In some embodiments, the product comprises a purified bis(aromatic) metal complex and less than 10% impurities.

[0005] Some embodiments of the present disclosure are directed to a method. In some embodiments, the method comprises 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 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.

[0006] In some embodiments of the present disclosure, a method is provided. In some embodiments, the method comprises 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; performing a post-synthesis aqueous extraction to purify the reaction mixture and obtain a product.

[0007] Some embodiments of the present disclosure relate to a method. In some embodiments, the method comprises one or more of the following steps: obtaining a reaction mixture comprising a bis(aromatic) metal complex and at least one impurity; and contacting the reaction mixture comprising the bis(aromatic) metal complex with a separation medium to obtain a product. In some embodiments, the product comprises a purified bis(aromatic) metal complex. In some embodiments, the product comprises at least one impurity that is less than the reaction mixture comprising the bis(aromatic) metal complex on a weight basis.

[0008] Some embodiments of the present disclosure relate to a composition comprising a bis(arylene) metal complex of the formula:

[0009]

[0010] Where: 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; wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 The two of them are optionally bonded to form a 6-membered aromatic group; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; wherein R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Some embodiments of the present disclosure are described with reference to the accompanying drawings by way of example only. With specific reference to the details of the accompanying drawings, it should be emphasized that the embodiments shown are by way of example and for the purpose of illustrative discussion of embodiments of the present disclosure. In this regard, the description and the accompanying drawings are Figure 1 It will make it apparent to those skilled in the art how the embodiments of the present disclosure can be implemented.

[0012] Figure 1Flowchart depicting a non-limiting embodiment of a method according to some embodiments.

[0013] Figure 2 Flowchart depicting a non-limiting embodiment of a method according to some embodiments.

[0014] Figure 3 Schematic diagram depicting a non-limiting example of a reaction scheme according to some embodiments.

[0015] Figures 4A to 4B Depicts the solution after passing through a column containing neutral alumina according to some embodiments 1 H NMR spectrum ( Figure 3 A) and previous 1 H NMR spectrum ( Figure 3 B).

[0016] Figures 5A to 5B Depicts the solution after passing through a column containing neutral alumina according to some embodiments 27 Al NMR spectrum ( Figure 4A ) and the previous 27 Al NMR spectrum ( Figure 4B ).

[0017] Figures 6A to 6C Stack showing crude product according to some embodiments 1 H NMR spectrum.

[0018] Figures 7A to 7B The crude product after aluminum reduction and continuous magnesium reduction according to some embodiments is shown. 1 H NMR.

[0019] Figures 8A to 8B The crude product after aluminum reduction and continuous magnesium reduction according to some embodiments is shown. 27 Al NMR.

[0020] Fig. 9 Schematic diagram depicting a non-limiting example of a reaction scheme according to some embodiments.

[0021] Fig.10 Shown is a thermogravimetric analysis ("TGA") of the product after aqueous extraction following synthesis according to some embodiments.

[0022] Fig.11 Shown is a TGA of a post-synthesis aqueous extraction according to some embodiments. DETAILED DESCRIPTION

[0023] Among those benefits and improvements disclosed, other objects and advantages of the present disclosure will become apparent from the following description in conjunction with the accompanying drawings. Detailed embodiments of the present disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the present disclosure that can be embodied in various forms. In addition, the examples given of various embodiments of the present disclosure are intended to be illustrative rather than limiting.

[0024] Any prior patents and publications cited herein are hereby incorporated by reference in their entirety.

[0025] Throughout this specification and claims, unless the context clearly dictates otherwise, the following terms have the meanings clearly associated with them herein. As used herein, the phrases "in one embodiment," "in an embodiment," and "in some embodiments" do not necessarily refer to the same embodiment, although they may be the same embodiment. In addition, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to the same embodiment, although they may be the same embodiment. All embodiments of the present disclosure are intended to be combined without departing from the scope or spirit of the present disclosure.

[0026] As used herein, the term "based on" is not exclusive and allows for being based on additional factors not described, unless the context clearly dictates otherwise. In addition, throughout this specification, the meanings of "a", "an", and "the" include plural referents. The meaning of "in..." includes "in..." and "at...".

[0027] As used herein, the term "alkyl" refers to a hydrocarbon chain group having 1 to 30 carbon atoms. The alkyl group may be connected via a single bond. An alkyl group having n carbon atoms may be designated as "C n Alkyl groups are grouped as follows. For example, "C3 alkyl" may include n-propyl and isopropyl. Alkyl groups having a range of carbon atoms, such as 1 to 30 carbon atoms, may be named C1-C 30 In some embodiments, the alkyl group is a linear group. In some embodiments, the alkyl group is a branched group. In some embodiments, the alkyl group is substituted. In some embodiments, the alkyl group is unsubstituted. In some embodiments, the alkyl group may include, consist of, or consist essentially of, or may be selected from the group consisting of: C1-C 12 Alkyl, C1-C 11 Alkyl, C1-C 10In some embodiments, the alkyl group may include, consist of, or consist essentially of, or may be selected from the group consisting of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, isobutyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, octyl, decyl, dodecyl, at least one of octadecyl or any combination thereof.

[0028] 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, 1-hexenyl, At least one of 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, and linolenyl, or any combination thereof.

[0029] 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 include, but are not limited to, at least one of ethynyl, propynyl, n-butynyl, n-pentynyl, 3-methyl-1-butynyl, n-hexynyl, methylpentynyl, or any combination thereof.

[0030] As used herein, the term "cycloalkyl" refers to a non-aromatic carbocyclic ring having 3 to 8 carbon atoms in the ring. The term includes monocyclic non-aromatic carbocyclic rings and polycyclic non-aromatic carbocyclic rings. For example, two or more cycloalkyl groups can be fused, bridged, or fused and bridged to obtain polycyclic non-aromatic carbocyclic rings. In some embodiments, the cycloalkyl group includes, consists of, or is substantially composed of, or is selected from a group consisting of: at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or any combination thereof.

[0031] As used herein, the term "aromatic hydrocarbon" refers to a monocyclic or polycyclic aromatic hydrocarbon compound including carbon and hydrogen atoms. In certain embodiments, the aromatic hydrocarbon has 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" refers to an aromatic hydrocarbon with a single aromatic ring structure when used as a modifier. The term "polycyclic" refers to an aromatic hydrocarbon with more than one aromatic ring structure (which may be a fused, bridged, spirocyclic or otherwise bonded ring structure) when used as a modifier. In certain embodiments, the terms aromatic hydrocarbon and aryl are used interchangeably.

[0032] Non-limiting examples of aromatic hydrocarbons include, but are not limited to, at least one of benzene, toluene, xylenes (e.g., o-xylene, m-xylene, p-xylene), tert-butyltoluene (e.g., o-tert-butyltoluene, m-tert-butyltoluene, p-tert-butyltoluene), ethylmethylbenzene (e.g., 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene), 1-isopropyl-4-methylbenzene, 1-tert-butyl-4-methylbenzene, mesitylene, unimellitolene, anthracene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene (e.g., 1,4-diethylbenzene), triethylbenzene, propylbenzene, butylbenzene, isobutylbenzene, sec-butylbenzene, tert-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenylene, dimethylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomers thereof, or any combination thereof, and the like.

[0033] Figure 1 is a flow chart of a method 100 for making a bis(arylene) metal complex according to some embodiments. Figure 1 As shown in , the method for manufacturing a bis(aryl) metal complex includes one or more of the following: wherein 102 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; 104 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(aryl) metal complex; and 106 contacting the reaction mixture including the bis(aryl) metal complex with a separation medium to obtain a product, the product including a purified bis(aryl) metal complex and less than 10% impurities. It should be understood that the method 100 includes any combination of at least two of step 102, step 104, and step 106, or any combination thereof.

[0034] In step 102, in some embodiments, the method 100 of making the 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.

[0035] In another embodiment of the present disclosure, a method for preparing a bis(arylene) metal complex is described in Figure 2 .like Figure 2 As shown in , the method for making a bis(aryl) metal complex includes one or more of the following: wherein 202 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; 204 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(aryl) metal complex; and 206 performing a post-synthesis aqueous extraction to obtain a product, the product including a purified bis(aryl) metal complex and less than 10% impurities. It should be understood that the method 200 includes any combination of at least two of step 202, step 204, and step 206, or any combination thereof.

[0036] refer to Figure 1 and Figure 2 In the method, 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 2 In some embodiments, the first temperature is not greater than a decomposition temperature of at least one of the metal halide, the first metal component, the aluminum halide, the first solvent, the intermediate complex, or any combination thereof.

[0037] The contacting may directly or indirectly include at least one of reduction, reaction, introduction, heating, or any combination thereof. In some embodiments, the contacting includes contacting at least one of the metal halide, the first metal component, the aluminum halide, the first solvent, or any combination thereof. In some embodiments, the contacting includes reacting at least one of the metal halide, the first metal component, the aluminum halide, the first solvent, or any combination thereof. In some embodiments, the contacting includes heating at least one of the metal halide, the first metal component, the aluminum halide, the first solvent, or any combination thereof. In some embodiments, the contacting includes reducing at least one of the metal halide, the first metal component, the aluminum halide, the first solvent, or any combination thereof.

[0038] 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 MoCl2, MoCl3, MoCl4, MoCl5, MoCl6, or any combination thereof. In some embodiments, the metal halide includes at least one of CrCl2, CrCl3, or any combination thereof. In some embodiments, the metal halide includes at least one of WCl2, WCl3, WCl4, WCl5, WCl6, or any combination thereof. In some embodiments, the metal halide includes at least one of MoCl2, MoCl3, MoCl4, MoCl5, MoCl6, CrCl2, CrCl3, WCl2, WCl3, WCl4, WCl5, WCl6, or any combination thereof. In some embodiments, the metal halide includes WCl2, WCl3, WCl 4 , WCl5, WCl6, WBr2, WBr3, WBr4, WBr5, WBr6, WI2, WI3, WI4, WI5, WI6, MoCl2, MoCl3, MoCl4, MoCl5, MoBr2, MoBr3, MoBr4, MoBr5, MoI2, MoI3, MoI4, MoI5, or any combination thereof. In some embodiments, the metal halide comprises a transition metal. In some embodiments, for example, the metal halide comprises 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.

[0039] 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, granules, or ingots. 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 aluminum-magnesium alloy powder. In some embodiments, the first metal component includes at least one of iron powder, nickel powder, or any combination thereof.

[0040] The first metal component may have an average particle size. The average particle size may 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 50nm to 100μm. For example, in some embodiments, the first metal component has an average particle size in the range of 20μm to 100μm, 1μm to 5μm, 50nm to 900nm, or any combination thereof or any range or sub-range therebetween.

[0041] 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, a hydrated form thereof, or any combination thereof. Examples of aluminum bromide include, but are not limited to, at least one of AlBr2, AlBr3, a hydrated form thereof, or any combination thereof. Examples of aluminum iodide include, but are not limited to, at least one of AlI2, AlI3, a hydrated form thereof, or any combination thereof.

[0042] The first solvent may include an aromatic hydrocarbon. For example, the first solvent may include an aromatic solvent. In some embodiments, the first solvent includes a compound of the formula:

[0043]

[0044] in:

[0045] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; or

[0046] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of them are optionally bonded to form a 6-membered aromatic group.

[0047] In some embodiments, the first solvent comprises a compound of the formula:

[0048]

[0049] in:

[0050] R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0051] Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

[0052] In some embodiments, the first solvent does not include heteroatoms. In some embodiments, the first solvent does not include halides.

[0053] In some embodiments, the first solvent includes at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, o-tert-butyltoluene, m-tert-butyltoluene, p-tert-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-tert-butyl-4-methylbenzene, mesitylene, unimellitolylene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, isobutylbenzene, sec-butylbenzene, tert-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenyl, dimethylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomer thereof, or any combination thereof. In some embodiments, the first solvent includes alkyl-substituted benzene. In some embodiments, the first solvent includes aryl-substituted benzene. In some embodiments, the first solvent does not include heteroatoms (e.g., as ring atoms of aromatic hydrocarbons). In some embodiments, the first solvent does not include a halide substituent on the arene.

[0054] The resulting reaction mixture includes an intermediate complex. In some embodiments, the intermediate complex is a complex of 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 comprises [bis(toluene) molybdenum] + [AlCl4] - .

[0055] refer to Figure 1 In step 104, in some embodiments, the method 100 for making the bis(arylene)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(arylene)metal complex.

[0056] The contacting may indirectly or directly include at least one of reduction, reaction, heating, introduction, 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 including the second solvent, 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 including 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 including 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 including the second solvent, or any combination thereof.

[0057] The contacting may be performed 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 a temperature in the range of 0°C to 150°C. In some embodiments, the second temperature is 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, A temperature in the range of 140°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 any range or sub-range between 0°C to 150°C.

[0058] 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 the form of a powder, granules or ingots. 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 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.

[0059] The second metal component may have an average particle size. The average particle size may 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 50nm to 100μm. For example, in some embodiments, the second metal component has an average particle size in the range of 20μm to 100μm, 1μm to 5μm, 50nm to 900nm, or any combination thereof or any range or sub-range therebetween.

[0060] The second solvent may include an ether-containing solvent. In some embodiments, the second solvent includes a reducing solvent. In some embodiments, the second solvent includes a solvent having a boiling point sufficient to allow the solvent to be removed at a temperature below the sublimation temperature of the bis(aromatic) metal complex under vacuum. For example, in some embodiments, the solvent has a boiling point of less than 150°C, less than 140°C, less than 130°C, less than 120°C, or less than 110°C. In some embodiments, the second solvent includes a solvent having an ether bond. In some embodiments, the second solvent includes at least one of tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane (DME), triethylene glycol dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, methyl tert-butyl ether (MTBE) or any combination thereof. In some embodiments, the second solvent includes an 80 / 20 mixture of dimethoxyethane (DME) and tetrahydrofuran (THF). In some embodiments, the second solvent may include a solvent for dissolving the bis(aromatic) metal complex. In some embodiments, for example, the second solvent includes at least one of toluene, hexane, or any combination thereof.

[0061] The resulting reaction mixture may include the bis(aryl) metal complex. In some embodiments, the bis(aryl) metal complex is a bis(first solvent) metal complex. In some embodiments, the bis(aryl) metal complex includes a compound of the formula:

[0062]

[0063] in:

[0064] M is Mo, Wo or Cr;

[0065] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0066] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group;

[0067] R 7 , R 8 , R 9 , R 10 , R 11 and R 12are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0068] Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

[0069] In some embodiments, the bis(aromatic) metal complex comprises 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(parametrelene) metal complex, a bis(benzene) 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. ) metal complex, bis(butylbenzene) metal complex, bis(isobutylbenzene) metal complex, bis(sec-butylbenzene) metal complex, bis(tert-butylbenzene) metal complex, bis(hexylbenzene) metal complex, bis(styrene) metal complex, bis(naphthalene) metal complex, bis(anthracene) metal complex, bis(phenanthrene) metal complex, bis(biphenyl) metal complex, bis(terphenyl) metal complex, bis(methylnaphthalene) metal complex, bis(biphenyl) metal complex, bis(dimethylnaphthalene) metal complex, bis(methylanthracene) metal complex, bis(4,4'-dimethylbiphenyl) metal complex, bis(bibenzyl) metal complex, bis(diphenylmethane) metal complex, any isomers thereof, or any combination thereof.

[0070] In some embodiments, the reaction mixture including the bis(arene)metal complex includes no more than 50 weight percent of at least one impurity, based on the total weight of the reaction mixture including the bis(arene)metal complex. In some embodiments, the reaction mixture including the bis(aromatic) metal complex includes 0.01 wt% to 50 wt%, 0.01 wt% to 45 wt%, 0.01 wt% to 40 wt%, 0.01 wt% to 35 wt%, 0.01 wt% to 30 wt%, 0.01 wt% to 25 wt%, 0.01 wt% to 20 wt%, 0.01 wt% to 15 wt%, 0.01 wt% to 10 wt%, 5 wt% to 50 wt%, 10 wt% to 50 wt%, 15 wt% to 50 wt%, 20 wt% to 50 wt%, 25 wt% to 50 wt%, 30 wt% to 50 wt%, 35 wt% to 50 wt%, 40 wt% to 45 wt%, or 45 wt% to 50 wt% of at least one impurity based on the total weight of the reaction mixture including the bis(aromatic) metal complex. In some embodiments, the impurities include at least one of aluminum halide impurities, coupled aromatic impurities, polyaromatic impurities, or any combination thereof. In some embodiments, the impurities include at least one of aluminum halide, tetrahydrofuran coordinated with aluminum halide, coupled aromatic compounds (e.g., dimethylbiphenyl compounds), or any combination thereof. In some embodiments, the coupled aromatic compounds include compounds of the formula:

[0071]

[0072] Where: R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl.

[0073] In some embodiments, the reaction mixture comprising the bis(aryl)metal complex does not include a compound of 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 comprising the bis(aryl) metal complex does not include [AlCl2(THF)4] +[AlCl4] - In some embodiments, the reaction mixture comprising the bis(arylene) metal complex does not contain a detectable amount of [AlCl2(THF)4] + [AlCl4] - .

[0074] refer to Figure 1 In step 106, in some embodiments, the method 100 for making the bis(arylene) metal complex comprises contacting a reaction mixture comprising the bis(arylene) metal complex with a separation medium to obtain a product. In some embodiments, the product comprises a purified bis(arylene) metal complex and optionally at least one impurity.

[0075] The reaction mixture comprising the bis(aromatic) metal complex may be contacted with a separation medium. The contacting may comprise passing the reaction mixture comprising the bis(aromatic) metal complex through a column containing a separation medium sufficient to allow the separation medium to remove at least a portion of the impurities present in the reaction mixture comprising the bis(aromatic) metal complex. In some embodiments, prior to the contacting, the method further comprises at least one of the following steps: filtering the reaction mixture comprising the bis(aromatic) metal complex to obtain a filtered reaction mixture; drying the reaction mixture comprising the bis(aromatic) metal complex to obtain a dried reaction mixture; contacting the reaction mixture comprising the bis(aromatic) metal complex with an extraction solvent to obtain an extracted reaction mixture; filtering an 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 comprises at least one of hexane, pentane, or any combination thereof.

[0076] The separation medium may be suitable for separating (e.g., absorbing, adsorbing, absorbing, etc.) at least one impurity from a reaction mixture comprising the bis(aromatic) metal complex. In some embodiments, the separation medium comprises at least one of neutral alumina, acidic alumina, basic alumina, florisil, silicon dioxide, or any combination thereof. In some embodiments, the separation medium comprises magnesium silicate. In some embodiments, the magnesium silicate is a compound of the formula MgO:XSiO2, wherein X is 1 to 10. In some embodiments, the magnesium silicate is hydrated and is a compound of the formula MgO:XSiO2·H2O, wherein X is 1 to 10.

[0077] The separation medium may have an average particle size. The average particle size may 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 sub-range therebetween.

[0078] refer to Figure 2 In some embodiments of the present disclosure, the reaction mixture including the bis(arene)metal complex may be subjected to post-synthesis aqueous extraction to obtain a resulting purified product.

[0079] In certain embodiments of the present disclosure, the post-synthesis aqueous extraction comprises methods known in the relevant art. For example, one method of post-aqueous extraction comprises drying the reaction mixture comprising the bis(aromatic) metal complex from step 204 to obtain a dried reaction mixture; this may partially dry the reaction mixture comprising the bis(aromatic) metal complex to obtain a partially dried reaction mixture; contacting the dried or partially dried reaction mixture comprising the bis(aromatic) 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.

[0080] In some embodiments of the present disclosure, the organic extracted reaction mixture may be cooled to a range of -15 to 15°C, in other embodiments, it may be -10 to 10°C and any variations therebetween.

[0081] In some embodiments of the present disclosure, the extraction solvent may be an aromatic solvent. For example, in some embodiments, the aromatic solvent includes at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, o-tert-butyltoluene, m-tert-butyltoluene, p-tert-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-tert-butyl-4-methylbenzene, mesitylene, unsymmetrical trimethylbenzene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, isobutylbenzene, sec-butylbenzene, tert-butylbenzene, and hexylbenzene, or any combination thereof.

[0082] In some embodiments of the present disclosure, the extraction solvent may be an aliphatic solvent. For example, in some embodiments, the aliphatic solvent includes at least one of hexane, pentane, heptane, octane, cyclohexane, methylcyclohexane, or any combination thereof.

[0083] In some embodiments of the present disclosure, Figure 2 After step 204 in the present invention, the reaction mixture can be further purified by using a separation medium as described in the present disclosure.

[0084] In embodiments described in the present disclosure, the product may include the purified bis(aromatic) metal complex and at least one impurity that is less than the reaction mixture (e.g., which is in contact with the separation medium) including the bis(aromatic) metal complex on a weight basis. The product may include no more than 10% impurities. In some embodiments, for example, the product includes no more than 9% impurities, no more than 8% impurities, no more than 7% impurities, no more than 6% impurities, no more than 5% impurities, no more than 4% impurities, no more than 3% impurities, no more than 2% impurities, no more than 1.9% impurities, no more than 1.8% impurities, no more than 1.7% impurities, no more than 1.6% impurities, no more than 1.5% impurities, no more than 1.4% impurities, no more than 1.3% impurities, no more than 1.2% impurities, no more than 1.1% impurities, no more than 1% impurities, no more than 0.9% impurities, no more than 0.8% impurities, no more than 0.7% impurities, no more than 0.6% impurities, no more than 0.5% impurities, no more than 0.4% impurities, no more than 0.3% impurities, no more than 0.2% impurities, or no more than 0.1% impurities.

[0085] In some embodiments, the product comprises 0.01% to 10% impurities, 0.1% to 2% impurities, 0.1% to 1.9% impurities, 0.1% to 1.8% impurities, 0.1% to 1.7% impurities, 0.1% to 1.6% impurities, 0.1% to 1.5% impurities, 0.1% to 1.4% impurities, 0.1% to 1.3% impurities, 0.1% to 1.2% impurities, 0.1% to 1% impurities, 0.1% to 0.9% impurities, 0.1% to 0.8% impurities, 0.1% to 0.7% impurities, 0.1% to 0.6% impurities, 0.1% to 0. 5% impurities, 0.1% to 0.4% impurities, 0.1% to 0.3% impurities, 0.2% to 2% impurities, 0.3% to 2% impurities, 0.4% to 2% impurities, 0.5% to 2% impurities, 0.6% to 2% impurities, 0.7% to 2% impurities, 0.8% to 2% impurities, 0.9% to 2% impurities, 1% to 2% impurities, 1.1% to 2% impurities, 1.2% to 2% impurities, 1.3% to 2% impurities, 1.4% to 2% impurities, 1.5% to 2% impurities, 1.6% to 2% impurities, 1.7% to 2% impurities, or 1.8% to 2% impurities. In some embodiments, the product comprises 27 Undetectable levels of aluminum halide as determined by Al NMR spectroscopy.

[0086] 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 ether-containing solvents, anionic aryl molybdenum "salt" complexes, aluminum halide impurities, coupled aromatic impurities, polyaromatic impurities, or any combination thereof. In some embodiments, the impurities include at least one of aluminum halide, tetrahydrofuran coordinated with aluminum halide, coupled aromatic compounds (e.g., dimethylbiphenyl compounds), methylene-bridged diaromatic compounds, or any combination thereof. In some embodiments, the coupled aromatic compounds include compounds of the formula:

[0087]

[0088] Where: R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl.

[0089] In some embodiments, the impurities include compounds of the formula

[0090]

[0091] 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 Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl.

[0092] The presence and type of impurities (including the amount of impurities) can be measured using 1 H NMR spectroscopy, 27 Al NMR spectroscopy or any combination thereof. In some embodiments, the product comprises 27 Undetectable levels of aluminum halide as determined by Al NMR spectroscopy.

[0093] Example 1

[0094] Molybdenum pentachloride (MoCl5), anhydrous aluminum chloride (AlCl3) and aluminum powder (A 0 ). Toluene is added and the mixture is stirred and heated to reflux in a hot bath at about 110°C. After 40 hours, the mixture is cooled to about 40°C and tetrahydrofuran is slowly added. The mixture is heated in a hot bath (heating it to about 100°C for about 15 hours) to reflux, then cooled to ambient and filtered to remove excess aluminum powder. The filtrate is washed with pentane and evaporated to dryness under vacuum (0.1 Pa). The residue is then extracted with boiling pentane and the extract is filtered and concentrated. The solution containing the extract is passed through a column filled with neutral alumina to obtain a bis(toluene) molybdenum complex. A schematic diagram of the reaction scheme is shown in Figure 3 middle. Figures 4A to 4B After passing the solution through the column, 1 H NMR spectrum ( Figure 4A ) and the previous 1 H NMR spectrum ( Figure 4B ).exist Figure 4A , the broadening of the aromatic resonances is indicated by reference numeral 302 . Figures 5A to 5B Present the solution before passing through the column 27 Al NMR spectrum ( Figure 5A ) and later 27 Al NMR spectrum ( Figure 5B ).exist Figure 5A , the probe background peak is indicated by reference number 402 .

[0095] Example 2

[0096] Solvent and reaction time of bis(toluene) platinum synthesis are different.100mL round-bottom flask is equipped with magnetic stirring egg through PTFE coating and is equipped with platinum pentachloride (3.00g, 10.9mmol, 1.00 equivalent), aluminum chloride (1.66g, 12.5mmol, 1.15 equivalent), -325 mesh aluminum powder (0.439g, 16.3mmol, 1.50 equivalent), toluene (29.1g, 316mmol, 29 equivalent) and dodecane (18.5g, 109mmol, 10 equivalent).Described mixture is stirred 30 minutes so that initial exotherm (10 ℃ to 20 ℃) ​​disappears and then refluxes in 135 ℃ oil bath for 40 hours, causes the formation of two-phase reaction mixture.Described reaction mixture is cooled, and decant transparent light brown supernatant. To the remaining dark oily lower phase containing the intermediate [(toluene)2Mo][AlCl4], toluene (29 g), magnesium powder (1.58 g, 65.3 mmol, 6.00 equiv) and tetrahydrofuran (25.0 g) were added dropwise over about 10 minutes. The dark green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium porosity glass frit funnel. The green-brown filtrate was stripped of solvent under reduced pressure (100 mTorr) and then extracted with a 100 mL aliquot and a 50 ml aliquot of boiling hexane to give a green solution after filtration. The filtrate was concentrated under reduced pressure to give 3.90 g of a viscous green solid. The green solid was dissolved in a 50 / 50 mixture of toluene and hexane and then eluted through a 3 cm high, 4.5 cm diameter bed of neutral alumina, leaving a reddish-brown band on the alumina and producing an emerald green solution. The green product solution was concentrated under reduced pressure to a green solid to give 1.58 g (52%) of a 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 a green crystalline product.

[0097] 1 H NMR (400 MHz, d6-benzene, 298 K): δ 4.60 (br s, 5H), 1.86 (s, 3H) ppm. 13 C{ 1 H} NMR (100 MHz, d6-benzene, 289 K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.

[0098] Example 3

[0099] Solvent and reaction time of bis(toluene) platinum synthesis are different. A 100 mL round bottom flask is equipped with a PTFE coated magnetic stirring egg and is equipped with platinum pentachloride (3.00 g, 10.9 mmol, 1.00 equivalent), aluminum chloride (1.66 g, 12.5 mmol, 1.15 equivalent), -325 mesh aluminum powder (0.439 g, 16.3 mmol, 1.50 equivalent) and toluene (29.1 g, 316 mmol, 29 equivalent). The mixture is stirred for 30 minutes to dissipate the initial exotherm (10 ° C to 20 ° C) and then refluxed in an oil bath at 135 ° C for 40 hours, resulting in the formation of a two-phase reaction mixture. The reaction mixture is cooled and treated with magnesium powder (1.58 g, 65.3 mmol, 6.00 equivalent) and tetrahydrofuran (25.0 g) in a dropwise manner for about 10 minutes. The dark green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium porosity glass funnel. The green-brown filtrate was stripped of solvent under reduced pressure (100 mTorr), and then extracted with 100 mL aliquots 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 viscous green solid. The green solid was dissolved in a 50 / 50 mixture of toluene and hexane, and then eluted through a 3 cm high, 4.5 cm diameter neutral alumina bed, leaving a reddish-brown band on the alumina and producing an emerald green solution. The green product solution was concentrated under reduced pressure to a green solid to give 2.00 g (52%) of a 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 a green crystalline product. See NMR data: 1 H NMR (400 MHz, d6-benzene, 298 K): δ 4.60 (brs, 5H), 1.86 (s, 3H) ppm. 13 C{1H} NMR (100 MHz, d6-benzene, 289K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.

[0100] Example 4

[0101] Solvents and reaction times for bis(toluene)molybdenum synthesis were different. A similar process to Example 2 was performed except that the initial reflux time for the reaction step to form the [(toluene)2Mo][AlCl4] was 4 hours instead of 40 hours.

[0102] Examples 2 to 4 involve bis(toluene) molybdenum synthesis. In each of Examples 2 to 4, the solvent and reaction time are different. Table 1 below summarizes the solvents and reaction times used in each of Examples 2 to 4.

[0103] Table 1: Different solvents and reaction times for the synthesis of bis(toluene)molybdenum.

[0104]

[0105] Figure 5A 5C shows Example 2 ( Figure 5A )、Example 3( Figure 5B ) and the stack of the crude product of Example 4 ( FIG. 5C ) 1 H NMR spectrum. In FIG. 5C , 502 corresponds to the aromatic resonance of the product in combination with toluene and 504 corresponds to the resonance of the impurity coordinated with tetrahydrofuran. When a shorter reflux time is used, the relative amount of impurities present in the spectrum corresponding to Example 4 is much higher. In addition, the peak width corresponding to the aromatic resonance of the bis(toluene) molybdenum product is understood to be related to the presence of impurities, which are composed of molybdenum in combination with other aromatic impurities or other impurities present that can act as Lewis base ligands. As can be seen from the spectrum, in the 1 The crude product with the least impurities observed in H NMR was from Example 3. It is clear from the results that when aluminum is used instead of magnesium for the reduction of [(toluene)2Mo][AlCl4], elution from the alumina medium results in the removal of many other impurities present in addition to the tetrachloroaluminate.

[0106] Example 5

[0107] The hexane extract was treated with heat / vacuum for a 10 g scale bis(toluene)platinum synthesis. A 250 mL round bottom flask was equipped with a PTFE coated magnetic stirring egg and was loaded with platinum pentachloride (10.00 g, 36.6 mmol, 1.00 equiv), aluminum chloride (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 mol, 30 equiv). The mixture was stirred for 1 hour to allow the initial exotherm (15° C. to 20° C.) to subside and then refluxed in an oil bath at 135° C. for 40 hours, resulting in the formation of a two-phase reaction mixture. The reaction mixture was cooled and treated with magnesium powder (5.32 g, 219 mmol, 6.00 equiv) and tetrahydrofuran (84 g) in a dropwise manner over approximately 15 minutes. The dark green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium porosity glass frit funnel. The green-brown filtrate was stripped of solvent under reduced pressure (100 mTorr), extracted with 2 aliquots of 250 mL boiling hexanes, filtered hot on a medium porosity glass frit and then stripped of solvent under reduced pressure. The mixture was then filtered through a 1% ethanol solution. 1 H NMR analysis of the stripped hexane extracts, 1H NMR showed the presence of an impurity with resonances corresponding to coordinated tetrahydrofuran (δ 3.89 (br s, 2H), 1.35 (br s, 2H) ppm). The material was then heated in an oil bath at 100 °C under 100 mTorr vacuum for a total of 3.5 hours. The hexane extraction process was repeated followed by stripping under vacuum to give 12.07 g of a viscous green residue. The residue was purified by 1 H NMR analysis, 1 H NMR showed the disappearance of the resonance due to the tetrahydrofuran coordinated by the impurity, and the residue was also analyzed by TGA, which showed that about 46% by weight of the material (5.6 g) corresponded to the bis(toluene)platinum product. The residue was purified by vacuum sublimation in an oil bath at 115° C. to 140° C. at a pressure of 100 mTorr to give two sublimed fractions: 3.77 g and 2.17 g of the expected bis(toluene)platinum product (total yield 60%). TGA analysis of the two fractions indicated residues of 6.3% and 7.0%, respectively.

[0108] Good yields were achieved using magnesium as the reducing agent for the intermediate [(toluene)2Mo][AlCl4] and purification from the magnesium reduction product by sublimation was performed without affecting the yield.

[0109] Example 6

[0110] The synthesis of bis(toluene)platinum was carried out using aluminum and magnesium as continuous reducing agents. A 100 mL round bottom flask was equipped with a PTFE coated magnetic stirring egg and was equipped with platinum pentachloride (3.00 g, 10.9 mmol, 1.00 equivalent), aluminum chloride (1.66 g, 12.5 mmol, 1.15 equivalent), -325 mesh aluminum powder (1.17, 43.6 mmol, 4.00 equivalent), toluene (30.1 g, 327 mmol, 30 equivalent). The mixture was stirred for 1 hour to allow the initial exotherm (15° C. to 20° C.) to subside and then refluxed in an oil bath at 135° C. for 40 hours, resulting in the formation of a two-phase reaction mixture. The reaction mixture was cooled and then treated with tetrahydrofuran (25.0 g) in a dropwise manner for about 15 minutes. The dark green reaction mixture was heated to reflux for 18 hours, and a small amount of aliquots were removed, the solvent was stripped, and the mixture was stirred for 18 hours. The reaction mixture was stirred for 18 hours. The mixture was stirred for 20 minutes ... 1 H NMR and 27 Al NMR analysis was performed. 1 The H NMR spectrum exhibited resonances corresponding to the methyl groups of the toluene ligands 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 another 18 hours, filtered through a medium porosity glass frit funnel, and stripped of volatiles under reduced pressure. The green-brown filtrate was stripped of solvent under reduced pressure (100 mTorr), heated at 100° C. under vacuum for 15 minutes, and then extracted with a 100 mL aliquot and a 50 ml aliquot of boiling hexane to give a green solution after filtration. The green solution was stripped of solvent to give 3.24 g of a viscous green solid. The green solid was purified by 1 H NMR and 27 Al NMR analysis indicated the formation of the desired product in the absence of the impurity [AlCl2(THF)4][AlCl4]. 1 H NMR (400 MHz, d6-benzene, 298 K): δ 4.63 (d, 2H), 4.59 (t, 2H), 4.51 (t, 1H) 1.86 (s, 3H) ppm. 13 C{ 1 H} NMR (100 MHz, d6-benzene, 289K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.

[0111] Figures 6A to 6B The crude product after aluminum reduction according to some embodiments is shown 1 H NMR ( Fig. 6A ) and the crude product after continuous magnesium reduction 1 H NMR ( Figure 6B ). Figures 7A to 7B The crude product after aluminum reduction according to some embodiments is shown 27 AlNMR Fig. 7A ) and the crude product after continuous magnesium reduction 27 Al NMR Figure 7B ).

[0112] Example 7

[0113] The synthesis and batch purification comparison of bis(toluene) platinum on a 36g scale were carried out with aluminum as a reducing agent. Platinum pentachloride (36.0g, 131mmol, 1.00 equivalent), aluminum chloride (19.9g, 150mmol, 1.15 equivalent), -325 mesh aluminum powder (14.1g, 524mmol, 4.00 equivalent), toluene (350g, 3.80mol, 29 equivalent) were loaded into a 3-neck 1L round-bottom flask. The flask was equipped with a mechanical stirrer device (glass stirring rod, PTFE stirrer bearing, PTFE stirring paddle) and stirred at about 250RPM. The mixture was stirred for 30 hours so that the initial exotherm (5°C to 10°C) disappeared and then refluxed in an oil bath at 135°C for 40 hours, resulting in the formation of a two-phase reaction mixture. The reaction mixture was cooled, and then slowly treated with tetrahydrofuran (302g) for about 2 hours. The reaction mixture was then refluxed for 18 hours, allowed to cool, and filtered through a medium porosity glass frit funnel. The green-brown filtrate was stripped of solvent under reduced pressure (100 mTorr), extracted with 2 equal portions of 250 mL boiling hexane, filtered hot on a medium porosity glass frit and then stripped of solvent under reduced pressure to give 114 g of crude material. The crude product was extracted with boiling pentane (500 mL, 4x, 2 L total) and filtered to give a green solution. The solvent was evaporated from the solution under reduced pressure to give 20.10 g (crude yield from 55% pentane extraction) of a green solid. The green solid was purified by 1 H NMR and 27 Al NMR analysis showed the presence of [AlCl2(THF)4][AlCl4] impurities in addition to the product. The crude product extracted with pentane was then divided into 6 approximately equal masses and purified according to the method shown in Table 2 below. As shown in Table 2, passing the bis(aromatic) molybdenum complex through an adsorption medium was superior to recrystallization, at least in terms of purity and yield of the isolated product. It was also observed that sublimation of the impure product resulted in lower yields and lower purity.

[0114] Table 2

[0115]

[0116] Example 8

[0117] Independent synthesis of [AlCl2(THF)4][AlCl4]. Weigh 1.0 g AlCl3 (7.50 mmol, 1 equivalent) into a transparent 40 ml scintillation vial containing a micro stir bar. Add 10 ml of toluene to the vial and stir the mixture to dissolve the solid. Heat the reaction mixture and stir while adding 1.1 g (15.0 mmol, 2 equivalents) THF dropwise. The reaction mixture is heated at 100°C for two hours, and the solvent is allowed to evaporate slowly to give a colorless crystalline solid that is analyzed by NMR and shown to match the main aluminum species produced as an impurity in the synthesis of bis(toluene) molybdenum. See NMR data: 1 H NMR (400MHz, d6-benzene, 298K): δ3.58(s,2H), 0.88(s,2H)ppm. 13 C{1H}NMR (100 MHz, d6-benzene, 289K): δ 74.39, 24.67 ppm. 27 Al NMR (104 MHz, d6-benzene, 289 K): δ 104.0 ppm.

[0118] Example 9

[0119] The synthesis of bis(toluene) molybdenum was carried out on a 50 g scale from MoCl5. A 3 L round bottom flask was charged with molybdenum pentachloride (50.548 g, 185 mmol, 1.0 eq), aluminum chloride (56.176 g, 421 mmol, 2.28 eq) and aluminum powder (7.395 g, 274 mmol, 1.48 eq). Toluene (505 g, 5.48 mol, 29.6 eq) was charged into the flask and the reaction mixture was stirred at ambient temperature for 1 hour. The reaction mixture was stirred and heated at reflux for 24 h. The reaction mixture was cooled and then ice-cooled in an ice bath, and magnesium powder (31.13 g, 1.28 mol, 6.91 eq) and tetrahydrofuran (422 g) were added dropwise so that the internal temperature did not exceed 25 ° C. The reaction solution was heated to reflux (~86 ° C) for 18 hours and then allowed to cool to ambient temperature. The reaction mixture was filtered into a 2L round bottom flask and the residual salts were washed with 300mL of anhydrous toluene. The combined filtrate was stripped of solvent under reduced pressure to give a dark green-brown solid. The crude solid was extracted 2x with hot (50°C) anhydrous hexane (1224g aliquot and 578g aliquot) and filtered sequentially after each hot extraction to give a clear green product solution in hexane. The combined filtrate from the hot hexane wash was stripped of solvent to give 50.2g of product. The hexane extract product was dissolved in a solution of 300mL toluene and 200ml hexane, cooled to about 5°C in an ice bath, and treated dropwise with 60mL of degassed deionized water. This resulted in the formation of a light precipitate, which was filtered off using a medium porosity filter funnel. The purified filtrate was then stripped of toluene under reduced pressure to give 27.3g of a green solid, which was purified by 1 The purity was 92% by H NMR (quantitative comparison with hexamethyldisiloxane internal standard). TGA analysis of the product indicated a purity of 88% based on residual mass. 1 The yield was 49% with H NMR weighted purity.

[0120] Example 10

[0121] according to Fig. 9 The reaction scheme of FIG. 4 was used to synthesize bis(toluene)molybdenum from MoCl 4 on a 50 g scale.A 2L reaction flask was charged with MoCl4 (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 and then ice-cooled in an ice bath, and magnesium powder (28.0 g, 1.155 mol, 5.50 equiv) and tetrahydrofuran (484 g, 6.72 mol, 32.0 equiv) were added dropwise. The reaction solution was heated to reflux (~86°C) for 8 hours. It was then allowed to cool and stand for about 72 hours. The solvent was then distilled from the reaction mixture under reduced pressure to near dryness. The resulting green solid was then dissolved in about 500 mL of anhydrous toluene and filtered through a medium porosity glass frit funnel to give a green solution. The filtrate was then stripped of toluene under reduced pressure to give 79.36 g of a sticky green solid, which was filtered through 1 The purity was analyzed by H NMR (quantitative comparison with hexamethyldisiloxane internal standard) and by TGA, which indicated 49% and 50% purity, respectively. The sticky green solid was dissolved in about 400 mL of toluene, cooled to about 5°C in an ice bath, and then treated with 20 mL of degassed deionized water over 45 minutes with vigorous stirring so that the internal temperature did not exceed 20°C. This resulted in the formation of a light precipitate, which was filtered off using a medium porosity filter funnel. The purified filtrate was then stripped of toluene under reduced pressure to give 47.31 g of a green solid, which was purified by 1 The purity was 85% by H NMR analysis. The green solid was transferred to a sublimation apparatus and further purified by sublimation (120 to 140° C., 100 mTorr) to give 36.3 g of bis(toluene) molybdenum. 1 The purity was 94% by H NMR analysis and 97% by TGA analysis. Fig.10 as shown in .

[0122] Example 11

[0123] according to Fig. 9 Reaction schemeSynthesis of 10g scale of bis(toluene) molybdenum was carried out from molybdenum tetrachloride. In a 500mL 3-necked round-bottom flask, molybdenum tetrachloride (10g, 42.0mmol, 1.0 equivalent), aluminum chloride (9.99g, 75.0mmol, 1.79 equivalent), aluminum powder (1.30g, 48.3mmol, 1.15 equivalent) and toluene (116g, 1260mol, 30.0 equivalent) were added. The reaction mixture was stirred and heated to reflux for 44 hours. The reaction mixture was cooled, then ice-cold in an ice bath, magnesium powder (5.61g, 231mol, 5.50 equivalent) and about 100mL of anhydrous tetrahydrofuran were loaded dropwise, keeping the internal temperature below 20°C. The reaction was heated to reflux (~87°C) for 17 hours, and then cooled to ambient temperature. The solvent was then distilled out under reduced pressure until the mixture was nearly dry. The crude product was then extracted with 400 mL of toluene and filtered through a medium porosity glass frit into a 1 L flask. The residual salts were washed with four 100 mL aliquots of toluene and filtered continuously to give about 800 mL of a green product solution. The green product solution was cooled in an ice bath, stirred vigorously, and treated dropwise with 15 mL of degassed deionized water for 1 hour. The mixture was treated with about 5 g of anhydrous magnesium sulfate and then filtered to remove the precipitate. The filtrate was stripped of solvent under reduced pressure to give 11.15 g of bis(toluene)platinum, which was purified by 1 The purity was 82% (78% yield) by H NMR analysis. TGA analysis of the product showed 6% total residue and 85% volatile residue due to bis(toluene) molybdenum weight conversion, as shown in FIG. Fig.11 as shown in .

[0124] aspect

[0125] A number of aspects are described below. It should be appreciated that any one or more of the features listed in the following aspects may be combined with any one or more of the features in the other aspects.

[0126] Aspect 1.

[0127] A method comprising:

[0128] 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;

[0129] 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

[0130] Obtaining a product;

[0131] wherein the product comprises a purified bis(aromatic) metal complex having less than 10% impurities.

[0132] Aspect 2. The method according to aspect 1, wherein obtaining the product comprises performing a post-synthesis aqueous extraction on the reaction mixture.

[0133] Aspect 3. A method comprising:

[0134] 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;

[0135] contacting the intermediate complex with a second metal component in a reaction mixture comprising a second solvent, thereby forming a reaction mixture comprising a bis(arene)metal complex; and

[0136] contacting a reaction mixture comprising the bis(arene)metal complex with a separation medium to obtain a product,

[0137] The product comprises a purified bis(aromatic) metal complex and less than 10% impurities.

[0138] Aspect 4. The method according to aspects 1 to 3, wherein the contacting of the metal halide is carried out at a temperature of at least 50°C to 200°C.

[0139] Aspect 5. A method according to any one of aspects 1 to 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.

[0140] Aspect 6. A method according to any one of Aspects 1 to 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.

[0141] Aspect 7. The method according to any one of aspects 1 to 6, wherein the aluminum halide comprises at least one of aluminum chloride, aluminum bromide, aluminum iodide, or any combination thereof.

[0142] Aspect 8. The method according to any one of aspects 1 to 7, wherein the first solvent comprises a compound of the formula:

[0143]

[0144] in:

[0145] R 1 , R 2 , R 3 , R 4 , R5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; or

[0146] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of them are optionally bonded to form a 6-membered aromatic group.

[0147] Aspect 9. The method according to any one of aspects 1 to 7, wherein the first solvent comprises a compound of the formula:

[0148]

[0149] in:

[0150] R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0151] Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

[0152] Aspect 10. The method according to any one of aspects 1 to 9, wherein the first solvent is an aromatic solvent, and the solvent includes at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, o-tert-butyltoluene, m-tert-butyltoluene, p-tert-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-tert-butyl-4-methylbenzene, mesitylene, unimellitolene, anthracene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, isobutylbenzene, sec-butylbenzene, tert-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenyl, dimethylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomers thereof, or any combination thereof.

[0153] Aspect 11. The method according to any one of aspects 1 to 10, wherein the intermediate complex is a complex of the formula:

[0154] [Dual (first solvent) metal] +[Aluminum halide] - ,

[0155] wherein the metal is Mo, Cr or W;

[0156] wherein the halide is Cl, Br or I.

[0157] Aspect 12. The method according to any one of aspects 1 to 11, wherein the contacting of the intermediate complex is carried out at a temperature of 0°C to 150°C.

[0158] Aspect 13. A method according to any one of aspects 1 to 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.

[0159] Aspect 14. A method according to any one of aspects 1 to 13, wherein the second solvent is an ether-containing solvent, the solvent comprising at least one of tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane (DME), triethylene glycol dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, methyl tert-butyl ether (MTBE) or any combination thereof.

[0160] Aspect 15. The method according to any one of aspects 1 to 14, wherein the bis(aryl) metal complex comprises a compound of the formula:

[0161]

[0162] in:

[0163] M is Mo, Wo or Cr;

[0164] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0165] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group;

[0166] R 7 , R 8 , R 9 , R 10 , R 11 and R 12are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0167] Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

[0168] Aspect 16. The method according to any one of aspects 1 to 14, wherein the bis(aromatic) metal complex comprises at least 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(trimethylbenzene) metal complex, a bis(xylene) metal complex, a bis(trimethylbenzene) metal complex, a bis(ethylbenzene) metal complex, a bis(1,4-diethylbenzene) metal complex, a bis(trimethylbenzene) metal complex, a bis(ethylbenzene) metal complex, a bis(1,4-diethylbenzene) metal complex, a bis(trimethylbenzene) 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(trimethyl ... The invention also includes bis(ethylbenzene) metal complex, bis(propylbenzene) metal complex, bis(butylbenzene) metal complex, bis(isobutylbenzene) metal complex, bis(sec-butylbenzene) metal complex, bis(tert-butylbenzene) metal complex, bis(hexylbenzene) metal complex, bis(styrene) metal complex, bis(naphthalene) metal complex, bis(anthracene) metal complex, bis(phenanthrene) metal complex, bis(biphenyl) metal complex, bis(terphenyl) metal complex, bis(methylnaphthalene) metal complex, bis(biphenylene) metal complex, bis(dimethylnaphthalene) metal complex, bis(methylanthracene) metal complex, bis(4,4'-dimethylbiphenyl) metal complex, bis(bibenzyl) metal complex, bis(diphenylmethane) metal complex, any isomers thereof, or any combination thereof.

[0169] Aspect 17. The method according to any one of aspects 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.

[0170] Aspect 18. The method according to any one of aspects 1 to 17, wherein the product comprises 1% to 2% impurities.

[0171] Aspect 19. The method according to any one of aspects 1 to 18, wherein the product comprises 0.01% to 2% impurities.

[0172] Aspect 20. The method according to any one of aspects 1 to 19, wherein the impurity comprises at least one of an aluminum halide, tetrahydrofuran coordinated to an aluminum halide, a coupled aromatic compound, or any combination thereof.

[0173] Aspect 21. The method according to aspect 20, wherein the coupled aromatic compound comprises a compound of the formula:

[0174]

[0175] in:

[0176] R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl.

[0177] Aspect 22. A method according to any one of aspects 1 to 20, wherein the product comprises 27 Undetectable levels of aluminum halide as determined by Al NMR spectroscopy.

[0178] Aspect 23. A synthesis method comprising:

[0179] contacting a metal halide with a first metal component and an aluminum halide in a first solvent to form a reaction including an intermediate complex; and

[0180] The intermediate complex is contacted with a second metal component in a reaction mixture including a second solvent, thereby forming a reaction mixture including a bis(arene)metal complex.

[0181] Aspect 24. A method according to Aspect 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.

[0182] Aspect 25. A method according to any one of Aspects 23 to 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.

[0183] Aspect 26. The method according to any one of aspects 23 to 25, wherein the aluminum halide comprises at least one of aluminum chloride, aluminum bromide, aluminum iodide, or any combination thereof.

[0184] Aspect 27. The method according to any one of aspects 23 to 26, wherein the first solvent comprises:

[0185] The following compound:

[0186]

[0187] in:

[0188] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; or

[0189] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group; or

[0190] The following compound:

[0191]

[0192] in:

[0193] R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0194] Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

[0195] Aspect 28. The method according to any one of aspects 23 to 27, wherein the intermediate complex is a complex of the formula:

[0196] [Dual (first solvent) metal] + [Aluminum halide] - ,

[0197] wherein the metal is Mo, Cr or W;

[0198] wherein the halide is Cl, Br or I.

[0199] Aspect 29. A method according to any one of Aspects 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.

[0200] Aspect 30. A method according to any one of aspects 23 to 29, wherein the second solvent is an ether-containing solvent, the solvent comprising at least one of tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane (DME), triethylene glycol dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, methyl tert-butyl ether (MTBE) or any combination thereof.

[0201] Aspect 31. The method according to any one of aspects 23 to 30, wherein the bis(aryl) metal complex comprises a compound of the formula:

[0202]

[0203] in:

[0204] M is Mo, Wo or Cr;

[0205] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0206] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group;

[0207] R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0208] Where R 7 , R 8 , R 9, R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

[0209] Aspect 32. The method according to any one of aspects 23 to 31, wherein the reaction mixture comprising the bis(aryl) metal complex does not contain a detectable amount of [AlCl2(THF)4] + [AlCl4] - .

[0210] Aspect 33. A purification method comprising:

[0211] obtaining a reaction mixture comprising a bis(arene)metal complex and at least one impurity; and

[0212] contacting a reaction mixture comprising the bis(arene)metal complex with a separation medium to obtain a product,

[0213] wherein the product comprises a purified bis(aryl)metal complex,

[0214] wherein the product comprises at least one impurity which is less on a weight basis than a reaction mixture comprising the bis(arene)metal complex.

[0215] Aspect 34. The method according to aspect 33, wherein the bis(aryl) metal complex comprises a compound of the formula:

[0216]

[0217] in:

[0218] M is Mo, Wo or Cr;

[0219] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0220] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group;

[0221] R 7 , R 8 , R 9 , R 10 , R11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0222] Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

[0223] Aspect 35. The method according to any one of aspects 33 to 34, wherein the at least one impurity comprises at least one of a metal halide, an aromatic hydrocarbon coordinated to a metal halide, a metal halide complex, or any combination thereof.

[0224] Aspect 36. The method according to any one of aspects 33 to 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 coupled aromatic compound, or any combination thereof.

[0225] Aspect 37. The method according to any one of aspects 33 to 36, wherein the reaction mixture comprising the bis(arylene) metal complex does not contain a detectable amount of [AlCl2(THF)4] + [AlCl4] - .

[0226] Aspect 38. The method according to any one of aspects 33 to 37, wherein the reaction mixture comprising the bis(arylene)metal complex comprises a solvent for dissolving the bis(arylene)metal complex.

[0227] Aspect 39. The method according to any one of aspects 33 to 38, wherein the reaction mixture comprising the bis(aromatic) metal complex comprises at least one of toluene, hexane, or any combination thereof.

[0228] Aspect 40. The method according to any one of aspects 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.

[0229] Aspect 41. The method according to any one of aspects 33 to 40, wherein the product has no more than 10 wt% of at least one impurity based on the total weight of the product.

[0230] Aspect 42. The method according to any one of aspects 33 to 41, wherein the product has no more than 2 wt% of at least one impurity based on the total weight of the product.

[0231] Aspect 43. A composition comprising: a bis(aryl) metal complex of the formula:

[0232]

[0233] in:

[0234] M is Mo, Wo or Cr;

[0235] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0236] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group;

[0237] R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0238] Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

[0239] Aspect 44. The composition according to aspect 43, wherein the bis(aryl)metal complex comprises less than 10% impurities.

[0240] Aspect 45. The composition according to aspects 43 to 44, wherein the bis(aromatic) metal complex comprises less than 5% impurities.

[0241] Aspect 46. The composition according to aspects 43 to 45, wherein the bis(aryl)metal complex comprises less than 1% impurities.

[0242] Aspect 47. The composition according to aspects 43 to 46, wherein the impurity comprises at least one of an aluminum halide, tetrahydrofuran coordinated to an aluminum halide, a coupled aromatic compound, a methylene bridged aromatic hydrocarbon, or any combination thereof.

[0243] Aspect 48. The composition according to aspects 43 to 47, wherein the impurities comprise at least one of the following compounds:

[0244]

[0245] 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 and 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 Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; magnesium halide, aluminum halide, alkali metal halide, alkaline earth metal halide, aryl magnesium halide, aryl aluminum, aryl aluminum halide, aluminum halide tetrahydrofuran complex, aryl magnesium halide tetrahydrofuran complex, halogenated metal compound, anionic aryl metal complex with alkali metal cation, anionic aryl metal complex with alkaline earth metal cation, oligomeric metal compound composed of metal coordinated by the following compound:

[0246]

[0247] in:

[0248] M is Mo, Wo or Cr;

[0249] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl;

[0250] Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6Two of are optionally bonded to form a 6-membered aromatic group;

[0251] in:

[0252] 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

[0253] in:

[0254] 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 Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl.

[0255] It is to be understood that changes may be made in detail, particularly in matters of construction materials employed and in shape, size and arrangement of parts without departing from the scope of the present disclosure. This specification and described embodiments are examples, with the true scope and spirit of the invention being indicated by the following claims.

Claims

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 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; wherein the product comprises a purified bis(aromatic) metal complex having less than 10% impurities.

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

3. The method of claim 1, 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.

4. 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. 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 method according to claim 1, wherein the first solvent comprises a compound of the formula: in: R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; or Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of them are optionally bonded to form a 6-membered aromatic group.

7. The method according to claim 1, wherein the first solvent comprises a compound of the formula: in: R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

8. 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-tert-butyltoluene, m-tert-butyltoluene, p-tert-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-tert-butyl-4-methylbenzene, mesitylene, unimellitolene, anthracene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, isobutylbenzene, sec-butylbenzene, tert-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenyl, dimethylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomers thereof, or any combination thereof.

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

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

11. The process according to claim 10, wherein the product is additionally purified by using a separation medium.

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

13. The method of claim 1, wherein the bis(aryl)metal complex comprises a compound of the formula: in: 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; Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; wherein R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

14. The method of claim 1, wherein the bis(aromatic) metal complex comprises at least 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(trimethylbenzene) metal complex, a bis(xylene) metal complex, a bis(ethylbenzene) metal complex, a bis(1,4-diethylbenzene) metal complex, a bis(triethylbenzene) metal complex, The invention also includes bis(propylbenzene) metal complex, bis(butylbenzene) metal complex, bis(isobutylbenzene) metal complex, bis(sec-butylbenzene) metal complex, bis(tert-butylbenzene) metal complex, bis(hexylbenzene) metal complex, bis(styrene) metal complex, bis(naphthalene) metal complex, bis(anthracene) metal complex, bis(phenanthrene) metal complex, bis(biphenyl) metal complex, bis(terphenyl) metal complex, bis(methylnaphthalene) metal complex, bis(biphenyl) metal complex, bis(dimethylnaphthalene) metal complex, bis(methylanthracene) metal complex, bis(4,4'-dimethylbiphenyl) metal complex, bis(bibenzyl) metal complex, bis(diphenylmethane) metal complex, any isomers thereof, or any combination thereof.

15. A composition comprising: Bis(aryl)metal complex of the formula: in: 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; Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group; R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; Where R 7 , R 8 , R 9 , R 10 , R 11 and R 12 Two of them are optionally bonded to form a 6-membered aromatic group.

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

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

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

19. The composition of claim 16, wherein the impurities include at least one of aluminum halides, tetrahydrofuran coordinated to aluminum halides, coupled aromatic compounds, methylene bridged aromatics, or any combination thereof.

20. The composition of claim 16, wherein the impurities comprise at least one of the following compounds: in: 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 and 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 Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl; magnesium halide, aluminum halide, alkali metal halide, alkaline earth metal halide, aryl magnesium halide, aryl aluminum, aryl aluminum halide, aluminum halide tetrahydrofuran complex, aryl magnesium halide tetrahydrofuran complex, halogenated metal compound, anionic aryl metal complex with alkali metal cation, anionic aryl metal complex with alkaline earth metal cation, oligomeric metal compound composed of metal coordinated by the following compound: in: 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; Where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two of are optionally bonded to form a 6-membered aromatic group; in: 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 in: 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 Each is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or aryl.

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