Organometallic precursors and related methods

Abstract

Some embodiments relate to precursors, including intermediate precursors, and related methods. To produce the intermediate precursor, a mixture of bis(arene) metal complexes is combined with a first arene. The mixture of bis(arene) metal complexes first arene is heated and then cooled. Upon cooling, the bis(first arene) metal complexes precipitate out of solution to produce the high purity intermediate precursor. To produce the precursor, the bis(first arene) metal complexes are contacted with a second arene to produce the high purity precursor.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to organometallic precursors for deposition processes, methods for making organometallic precursors, and the like.

[0002] Priority This disclosure claims priority to U.S. Provisional Application No. 63 / 309,181, filed February 11, 2022, the contents of which are incorporated herein by reference. [Background technology]

[0003] Metal arene complexes are a class of organometallic compounds that are useful for a variety of applications. Some applications for which metal arene complexes are useful require highly purified forms of the metal arene complexes. However, traditional purification is difficult, expensive, time-consuming, and inefficient.

[0004] Summary of the Invention Some embodiments relate to a method for producing an intermediate precursor. In some embodiments, the method for producing an intermediate precursor comprises, consists of, or consists essentially of one or more of the following steps: combining a mixture of bis(arene) metal complexes with a first arene; heating the mixture of bis(arene) metal complexes and the first arene; and cooling the mixture of bis(arene) metal complexes and the first arene to precipitate the bis(first arene) metal complex.

[0005] In some embodiments, the boiling point of the arene of the bis(arene) metal complex is higher than the boiling point of the first arene.

[0006] In some embodiments, each of the bis(arene) metal complexes present in the mixture of bis(arene) metal complexes is independently a bis(arene) metal complex of the formula: TIFF0007733839000001.tif34170[In the formula, M is Cr, Mo, W, Fe, or V; Ar1 is an arene of the formula: TIFF0007733839000002.tif62170 (in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. and Ar2 is an arene of the formula: TIFF0007733839000003.tif62170 (in the formula, R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. is].

[0007] In some embodiments, the first arene is an arene of the formula: TIFF0007733839000004.tif61170[where, R a , R b , R c , R d , R e , and R f are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0008] In some embodiments, the heating comprises heating to a temperature of from 100°C to 200°C.

[0009] In some embodiments, the heating comprises heating at a pressure ranging from atmospheric pressure to 100 bar.

[0010] In some embodiments, cooling comprises exposing to ambient conditions.

[0011] In some embodiments, the bis(first arene)metal complex is a complex of the formula: TIFF0007733839000005.tif34170[In the formula, M is Cr, Mo, W, Fe, or V; Ar3 is an arene of the formula: TIFF0007733839000006.tif61170 (in the formula, R a , R b , R c , R d , R e , and R f are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. is].

[0012] In some embodiments, the mixture of bis(arene) metal complexes comprises at least one of benzeneethylbenzenemolybdenum, benzenediethylbenzenemolybdenum, ethylbenzenediethylbenzenemolybdenum (EBDEBMo), bis(ethylbenzene)molybdenum (BEBMo), bis(diethylbenzene)molybdenum (BDEBMo), or any combination thereof.

[0013] In some embodiments, the first arene comprises at least one of benzene, toluene, xylene, bibenzyl, diphenylmethane, or any combination thereof.

[0014] In some embodiments, the bis(first arene)metal complex is obtained in a yield of 50% or greater.

[0015] In some embodiments, the method further comprises separating the bis(first arene) metal complex by filtration to obtain a purified bis(first arene) metal complex having a purity of 90% or greater.

[0016] Some embodiments relate to a method for producing a precursor. In some embodiments, the method for producing a precursor comprises, consists of, or consists essentially of one or more of the following steps: combining a first arene with a mixture of a bis(arene) metal complex; heating the mixture of the first arene and the bis(arene) metal complex; cooling the mixture of the first arene and the bis(arene) metal complex to obtain the bis(first arene) metal complex; combining the bis(first arene) metal complex with a second arene; and heating the bis(first arene) metal complex and the second arene to obtain the bis(second arene) metal complex.

[0017] In some embodiments, the boiling point of the arene of the bis(arene) metal complex is higher than the boiling point of the first arene.

[0018] In some embodiments, the boiling point of the first arene of the bis(first arene) metal complex is less than the boiling point of the second arene.

[0019] In some embodiments, the second arene has the formula: TIFF0007733839000007.tif61170[where, R g , R h , R i , R j , R k , and R m are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl; or TIFF0007733839000008.tif54170[In the formula, Z is a bond, alkyl, heteroatom, or heteroalkyl; and R n , R o , R p , R q , R r , R s , Rt , R u , R v , and R w are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. arenes having at least one of:

[0020] In some embodiments, the second arene comprises at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0021] In some embodiments, the bis(secondary arene) metal complex has the formula: TIFF0007733839000009.tif34170 or TIFF0007733839000010.tif34170[In the formula, M is Cr, Mo, W, Fe, or V; Z is a bond, alkyl, heteroatom, or heteroalkyl; Ar4 is an arene of the formula: TIFF0007733839000011.tif61170 (in the formula, R g , R h , R i , R j , Rk , and R m are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. and Ar5 is an arene of the formula: TIFF0007733839000012.tif54170 (in the formula, R n , R o , R p , R q , and R r are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. and Ar6 is an arene of the formula: TIFF0007733839000013.tif54170 (in the formula, R s , R t , R u , R v , and R w are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. is] At least one of the following complexes is used.

[0022] Some embodiments relate to a precursor comprising a bis(secondary arene) metal complex, wherein the bis(secondary arene) metal complex is a liquid having a purity of at least 90%.

[0023] Some embodiments relate to compositions comprising a precursor. In some embodiments, the precursor has the formula: TIFF0007733839000014.tif34170 or TIFF0007733839000015.tif34170[In the formula, M is Cr, Mo, W, Fe, or V; Z is a bond, alkyl, heteroatom, or heteroalkyl; Ar4 is an arene of the formula: TIFF0007733839000016.tif61170 (in the formula, R g , R h , R i , R j , R k , and R m are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. and Ar5 is an arene of the formula: TIFF0007733839000017.tif54170 (in the formula, R n , R o , R p , R q , and R r are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. and Ar6 is an arene of the formula: TIFF0007733839000018.tif54170 (in the formula, R s , R t , R u , R v , and R w are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. is] wherein the precursor has a purity of 90% or greater.

[0024] In some embodiments, the precursor is a liquid having a purity of 99% or greater.

[0025] Some embodiments of the present disclosure will now be described, by way of example only, with reference to the accompanying drawings. While specific reference will now be made in detail to the drawings, it is emphasized that the embodiments are by way of example only and are for the purpose of illustrating embodiments of the present disclosure. In this regard, the specification, together with the drawings, will make apparent to those skilled in the art how embodiments of the present disclosure can be practiced. [Brief explanation of the drawings]

[0026] [Figure 1] 1 is a non-limiting embodiment of a method for producing precursors (including intermediate precursors) according to some embodiments. [Figure 2] 1 shows a non-limiting embodiment of a reaction scheme for producing a precursor according to some embodiments. [Figure 3] 1 is a 1H NMR spectrum of isolated bis(benzene)molybdenum, according to some embodiments.

[0027] Detailed Description Among these disclosed benefits and improvements, other objects and advantages of the present disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. While particular embodiments of the present disclosure are disclosed herein, it should be understood that the disclosed embodiments are merely illustrative of the present disclosure, which may take various forms. Moreover, each given example of various embodiments of the present disclosure is intended to be illustrative and not limiting of the invention.

[0028] All prior patents and publications referred to herein are incorporated by reference in their entirety.

[0029] Throughout this specification and the claims, the following terms have the meanings expressly associated therewith, unless the context clearly dictates otherwise. As used herein, the phrases "in one embodiment," "in an embodiment," and "in some embodiments" do not necessarily refer to one or more of the same embodiments, but may be the same embodiments. Furthermore, as used herein, the phrases "in another embodiment" and "in some embodiments" do not necessarily refer to different embodiments, but may be different embodiments. It is intended that all embodiments of the present disclosure can be combined without departing from the scope or spirit of the present disclosure.

[0030] As used herein, the term "alkyl" refers to a hydrocarbon compound having 1 to 30 carbon atoms. 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 (e.g., 1 to 30 carbon atoms) is sometimes referred to as C1-C 30 In some embodiments, the alkyl is linear. In some embodiments, the alkyl is branched. In some embodiments, the alkyl is substituted. In some embodiments, the alkyl is unsubstituted. In some embodiments, the alkyl is C1-C 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0031] As used herein, the term "arene" refers to a monocyclic or polycyclic aromatic hydrocarbon compound. The number of carbon atoms in an arene can range from 5 carbon atoms to 100 carbon atoms. In some embodiments, an arene has 5 to 20 carbon atoms. For example, in some embodiments, an arene 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. When used as a modifier, the term "monocyclic" refers to an arene having one aromatic ring structure. When used as a modifier, the term "polycyclic" refers to an arene having more than one aromatic ring structure, which may be a fused, bridged, spiro, or other linked ring structure. The term "alkyl-substituted arene" refers to an arene having one or more alkyl substituents. In some embodiments, an alkyl-substituted arene can include at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. Arenes may also be referred to herein as Ar.

[0032] Non-limiting examples of arenes include 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, ethylbenzene, diethylbenzene (e.g., The arenes include, but are not limited to, at least one of 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.

[0033] As used herein, the term "metal" refers to at least one of an alkali metal, an alkaline earth metal, a transition metal, a post-transition metal, a lanthanide, or any combination thereof. In some embodiments, for example, the metal comprises or is selected from the group consisting of a transition metal. In some embodiments, the metal comprises or is selected from the group consisting of a Group VIB metal. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), or any combination thereof. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), vanadium (V), or any combination thereof. In some embodiments, the metal is in ionic form, elemental form, or any combination thereof.

[0034] As used herein, a "bis(arene) metal complex" refers to any organometallic compound having at least two arene bonds (e.g., coordinate bonds) to a metal. Each arene can be independently substituted or unsubstituted. In some embodiments, a bis(arene) metal complex has only one substituted arene coordinated to the metal. For example, in some embodiments, a bis(arene) metal complex comprises benzeneethylbenzenemolybdenum, where ethylbenzene is the substituted arene. In some embodiments, a bis(arene) metal complex comprises two substituted arenes coordinated to the metal. For example, in some embodiments, a bis(arene) metal complex comprises bis(diethylbenzene)molybdenum, where diethylbenzene is the substituted arene. In some embodiments, a bis(arene) metal complex comprises two arenes coordinated to the metal, where the two arenes are the same and the two arenes are substituted or unsubstituted.

[0035] Non-limiting examples of bis(arene) metal complexes include bis(benzene)molybdenum, bis(benzene)tungsten, bis(toluene)molybdenum, bis(toluene)tungsten, bis(xylene)molybdenum, bis(xylene)tungsten, bis(ethylbenzene)molybdenum, bis(ethylbenzene)tungsten, bis(benzene)chromium, bis(ethylbenzene)chromium, bis(toluene)chromium, bis(mesitylene)chromium, bis(mesitylene)molybdenum, bis(tetralin)chromium, bis(diphenyl)chromium, bis(diphenyl)chromium, and bis(diphenyl)chromium. The bis(arene) metal complexes include, but are not limited to, at least one of bis(arene) molybdenum, bis(mesitylene) molybdenum, bis(mesitylene) tungsten, bis(benzene) iron, bis(toluene) iron, bis(xylene) iron, bis(xylene) iron, bis(mesitylene) iron, bis(durene) iron, bis(hexamethylbenzene) iron, bis(hexamethylbenzene) chromium, bis(benzene) vanadium, bis(toluene) vanadium, any bis(arene isomer) metal complex thereof, or any combination thereof.

[0036] As used herein, the term "based on" is not exclusive and allows for based on additional elements not described herein unless the context clearly dictates otherwise. Additionally, throughout the specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes the meanings of "in" and "on."

[0037] Some organometallic precursors useful in semiconductor fabrication processes require high purity. However, obtaining organometallic compounds at the required high purity can be challenging. Synthetic methods for bis(arene) metal complexes exhibit significant batch-to-batch variability, particularly in terms of both the reaction products and the amount of each product. In addition, due to alkyl and dialkyl rearrangements, the Fischer-Hafner synthesis of bis(ethylbenzene)molybdenum produces a mixture of bis(ethylbenzene)molybdenum and bis(diethylbenzene)molybdenum isomers. Approaches for isolating specific bis(arene) metal complexes from mixtures of bis(arene) metal complexes are either unavailable or difficult, expensive, time-consuming, and inefficient.

[0038] Some embodiments relate to intermediate precursors and methods for preparing precursors that overcome at least some of the above-mentioned problems. As described herein, it has been discovered that contacting a mixture of bis(arene) metal complexes with a first arene that has low electron donating properties and / or a lower boiling point than the arene of the bis(arene) metal complex can provide a highly pure bis(first arene) metal complex as an intermediate precursor. The limited solubility of the bis(first arene) metal complex unexpectedly allows for isolation of the bis(first arene) metal complex in the presence of the arene of the bis(arene) metal complex that has a relatively high boiling point and relatively high electron donating properties. The bis(first arene) metal complex can then be contacted with a second arene to provide a highly pure bis(second arene) metal complex as a precursor.

[0039] FIG. 1 illustrates a non-limiting embodiment of a method 100 for producing precursors (including intermediate precursors) according to some embodiments.

[0040] As shown in FIG. 1 , in some embodiments, method 100 comprises, consists of, or consists essentially of one or more of the following steps: combining 102 a mixture of bis(arene) metal complexes with a first arene; heating 104 the mixture of bis(arene) metal complexes and the first arene; cooling 106 the mixture of bis(arene) metal complexes and the first arene to precipitate the bis(first arene) metal complex; combining 108 the bis(first arene) metal complex with a second arene; and heating 110 the bis(first arene) metal complex and the second arene to obtain the bis(second arene) metal complex.

[0041] In some embodiments, method 100 is a method for producing an intermediate precursor. In some embodiments, method 100 for producing an intermediate precursor includes one or more of steps 102, 104, and 106, or consists of one or more of steps 102, 104, and 106, or consists essentially of one or more of steps 102, 104, and 106. In some embodiments, method 100 is a method for producing a precursor. In some embodiments, the method for producing a precursor includes one or more of steps 108 and 110, or consists of one or more of steps 108 and 110, or consists essentially of one or more of steps 108 and 110. In some embodiments, the method for producing the precursor comprises, consists of, or consists essentially of one or more of steps 102, 104, 106, 108, and 110.

[0042] In step 102, in some embodiments, the mixture of bis(arene) metal complexes is combined with a first arene.

[0043] The manner in which the mixture of bis(arene) metal complexes and the first arene are combined is not particularly limited. In some embodiments, the combining comprises contacting the mixture of bis(arene) metal complexes with the first arene. In some embodiments, the combining comprises mixing the mixture of bis(arene) metal complexes with the first arene. In some embodiments, the combining comprises supplying the mixture of bis(arene) metal complexes and the first arene, separately or together, to a reaction vessel. In some embodiments, the combining comprises flowing or feeding the mixture of bis(arene) metal complexes and the first arene, separately or together, to a reaction vessel. In some embodiments, the combining comprises introducing the mixture of bis(arene) metal complexes and the first arene, separately or together, to a reaction vessel. In other embodiments, the contacting comprises pouring, placing, adding, or any combination thereof, the mixture of bis(arene) metal complexes and the first arene to a reaction vessel.

[0044] The mixture of bis(arene) metal complexes can include one or more metal complexes. In some embodiments, the mixture of bis(arene) metal complexes is a reaction product mixture. For example, in some embodiments, the mixture of bis(arene) metal complexes is an initial mixture containing a mixture of bis(arene) metal complexes produced by at least one of Fischer-Hafner synthesis (FHS), Friedel-Crafts reaction, arene metathesis, or any combination thereof. It will be appreciated that other synthetic routes and reactions can be used to obtain the mixture of bis(arene) metal complexes without departing from the scope of the present disclosure.

[0045] In some embodiments, the mixture of bis(arene) metal complexes contains multiple different bis(arene) metal complexes. The number of different bis(arene) metal complexes present in the mixture is not particularly limited, and may include, for example, but not limited to, up to 100 different bis(arene) metal complexes. In some embodiments, the difference between the bis(arene) metal complexes is one or more substituents (or the number of one or more substituents) attached to the arene of the bis(arene) metal complex. In some embodiments, the difference between the bis(arene) metal complexes is the stereochemistry (or spatial configuration) of one or more substituents attached to the arene of the bis(arene) metal complex. For example, in some embodiments, the mixture of bis(arene) metal complexes contains at least one or more isomers of the bis(arene) metal complex. In some embodiments, the difference between the bis(arene) metal complexes is the metal of the bis(arene) metal complex. In some embodiments, the differences between the bis(arene) metal complexes are any combination of one or more of the aforementioned differences.

[0046] In some embodiments, each bis(arene) metal complex present in the mixture of bis(arene) metal complexes is independently a bis(arene) metal complex of the formula: TIFF0007733839000019.tif34170[In the formula, M is a metal, Ar1 is an arene, Ar2 is an arene, which may be the same as or different from Ar1.

[0047] In some embodiments, Ar1 is an arene of the formula: TIFF0007733839000020.tif62170[In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0048] In some embodiments, Ar1 is a substituted arene, an unsubstituted arene, or any combination thereof. In some embodiments, for example, Ar1 comprises at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. In some embodiments, alkyl is a C1-C 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0049] In some embodiments, for example, Ar1 comprises or is selected from the group consisting of at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0050] In some embodiments, Ar2 is an arene of the formula: TIFF0007733839000021.tif62170[In the formula, R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0051] In some embodiments, Ar2 is a substituted arene, an unsubstituted arene, or any combination thereof. In some embodiments, for example, Ar2 comprises at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. In some embodiments, alkyl is a C1-C 10Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0052] In some embodiments, for example, Ar2 comprises or is selected from the group consisting of at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0053] In some embodiments, the mixture of bis(arene) metal complexes includes at least one bis(arene) metal complex in which Ar1 and Ar2 are the same. In some embodiments, the mixture of bis(arene) metal complexes includes at least one bis(arene) metal complex in which Ar1 and Ar2 are different.

[0054] In some embodiments, the metal of the bis(arene) metal complex comprises or is selected from the group consisting of transition metals. In some embodiments, the metal comprises or is selected from the group consisting of Group VIB metals. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), or any combination thereof. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), vanadium (V), or any combination thereof.

[0055] The first arene (which may be substituted or unsubstituted) can comprise an arene that is different from one or more arenes of the bis(arene) metal complexes included in the mixture. For example, the first arene can have at least one of one or more different substituents, one or more different spatial arrangements, one or more different numbers of substituents, or any combination thereof.

[0056] The first arene can be selected based on one or more arenes of the bis(arene) metal complex contained in the mixture. That is, the first arene can be selected to have a boiling point lower than at least one (or all) of the arenes of the bis(arene) metal complex. For example, in some embodiments, the boiling point of the arene of the bis(arene) metal complex is higher than the boiling point of the first arene. The first arene can be selected to have lower electron-donating properties than at least one (or all) of the arenes of the bis(arene) metal complex. For example, in some embodiments, the arene of the bis(arene) metal complex has a higher number of substituents (and thus may have higher electron-donating properties) than the first arene. Thus, in some embodiments, the first arene can be selected to have a lower boiling point, a fewer number of substituents (or otherwise lower electron-donating properties), or any combination thereof, compared to the arene of the bis(arene) metal complex.

[0057] In some embodiments, the first arene is an arene of the formula: TIFF0007733839000022.tif61170[In the formula, R a , R b , R c , R d , R e , and R f are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0058] In some embodiments, the first arene is a substituted arene, an unsubstituted arene, or any combination thereof. In some embodiments, the first arene is or includes at least one alkyl-substituted arene. In some embodiments, for example, the first arene includes at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of C1-C 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0059] In some embodiments, for example, the first arene comprises or is selected from the group consisting of at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0060] In step 104, in some embodiments, the mixture of the bis(arene) metal complex and the first arene is heated.

[0061] The manner in which the mixture of bis(arene) metal complexes and the first arene are heated is not particularly limited. In some embodiments, the heating comprises heating the mixture of bis(arene) metal complexes and the first arene to a first temperature. In some embodiments, the heating comprises heating the mixture of bis(arene) metal complexes and the first arene at a first temperature. In some embodiments, the heating comprises heating the mixture of bis(arene) metal complexes and the first arene in an oven, a furnace, on a hot plate, or with other heating devices and / or apparatuses. In some embodiments, the heating comprises heating the mixture of bis(arene) metal complexes and the first arene in a warm fluid bath (e.g., a hot water bath). In some embodiments, the heating comprises contacting the mixture of bis(arene) metal complexes and the first arene with a fluid (e.g., a gas or vapor, a liquid, etc.) having a first temperature. In some embodiments, the heating comprises exposing the mixture of the bis(arene) metal complex and the first arene to a fluid (e.g., a gas or vapor, a liquid, etc.) having a first temperature.

[0062] The first temperature can be below the decomposition temperature (e.g., thermal decomposition temperature) of at least one of the bis(arene) metal complex, the first arene, or any combination thereof. The first temperature can be at or above a threshold temperature (e.g., a minimum reaction temperature). In some embodiments, the first temperature is in the range of 100°C to 200°C. For example, in some embodiments, the first temperature is a temperature in the range of 110°C to 200°C, 115°C to 200°C, 120°C to 200°C, 125°C to 200°C, 130°C to 200°C, 135°C to 200°C, 140°C to 200°C, 145°C to 200°C, 150°C to 200°C, 155°C to 200°C, 160°C to 200°C, 165°C to 200°C, 170°C to 200°C, 175°C to 200°C, 180°C to 200°C, 185°C to 200°C, 190°C to 200°C, 195°C to 200°C, or any combination thereof. In some embodiments, the first temperature is a temperature in the range of 100°C to 195°C, 100°C to 190°C, 100°C to 185°C, 100°C to 180°C, 100°C to 175°C, 100°C to 170°C, 100°C to 165°C, 100°C to 160°C, 100°C to 155°C, 100°C to 150°C, 100°C to 145°C, 100°C to 140°C, 100°C to 135°C, 100°C to 130°C, 100°C to 125°C, 100°C to 120°C, 100°C to 115°C, 100°C to 110°C, 100°C to 105°C, or any combination thereof.

[0063] In some embodiments, the heating is performed under vacuum. In some embodiments, the heating is performed under pressure. For example, the heating can be performed at a pressure ranging from atmospheric pressure to 100 bar. In some embodiments, the pressure is in the range of at least one of 1 bar to 100 bar, 10 bar to 100 bar, 20 bar to 100 bar, 30 bar to 100 bar, 40 bar to 100 bar, 50 bar to 100 bar, 60 bar to 100 bar, 70 bar to 100 bar, 80 bar to 100 bar, 90 bar to 100 bar, 1 bar to 90 bar, 1 bar to 80 bar, 1 bar to 70 bar, 1 bar to 60 bar, 1 bar to 50 bar, 1 bar to 40 bar, 1 bar to 30 bar, 1 bar to 20 bar, 1 bar to 10 bar, 1 bar to 5 bar, or any combination thereof.

[0064] In step 106, in some embodiments, the mixture of the bis(arene) metal complex and the first arene is cooled to provide the bis(first arene) metal complex.

[0065] The manner in which the mixture of bis(arene) metal complexes and the first arene are cooled is not particularly limited. In some embodiments, cooling comprises cooling the mixture of bis(arene) metal complexes and the first arene to a second temperature below the first temperature. In some embodiments, cooling comprises exposing the mixture of bis(arene) metal complexes and the first arene to ambient conditions (e.g., temperature, pressure, etc.). In some embodiments, cooling comprises immersing the mixture of bis(arene) metal complexes and the first arene in a cold fluid bath (e.g., a cold water bath). In some embodiments, cooling comprises contacting the mixture of bis(arene) metal complexes and the first arene with a fluid (e.g., gas or vapor, fluid, etc.) having a second temperature. In some embodiments, cooling comprises exposing the mixture of bis(arene) metal complexes and the first arene to a fluid (e.g., gas or vapor, fluid, etc.) having a second temperature.

[0066] As described above, the mixture of bis(arene) metal complex and the first arene is cooled to obtain the bis(first arene) metal complex. That is, upon cooling, the bis(first arene) metal complex can be formed, in which one or more arenes of the bis(arene) metal complex are replaced with the first arene. The bis(arene) metal complex can be recrystallized or precipitated (e.g., from solution) upon cooling, or any combination thereof. In some embodiments, the bis(first arene) metal complex is obtained as a solid. In some embodiments, the bis(first arene) metal complex is obtained as a liquid. In some embodiments, the bis(first arene) metal complex is obtained (e.g., isolated, recovered, etc.) by filtration. In some embodiments, the bis(first arene) metal complex is obtained by at least one of sublimation, distillation, or any combination thereof.

[0067] In some embodiments, the bis(first arene) metal complex comprises a complex of the formula: TIFF0007733839000023.tif34170[In the formula, M is a metal, Ar3 is the first arene.

[0068] In some embodiments, for example, Ar3 is an arene of the formula: TIFF0007733839000024.tif61170[In the formula, R a , R b , R c , R d , R e , and R f are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0069] In some embodiments, the first arene is a substituted arene, an unsubstituted arene, or any combination thereof. In some embodiments, the first arene is or includes at least one alkyl-substituted arene. In some embodiments, for example, the first arene includes at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of C1-C 10 Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0070] In some embodiments, for example, the first arene comprises or is selected from the group consisting of at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0071] In some embodiments, the metal of the bis(first arene)metal complex comprises or is selected from the group consisting of transition metals. In some embodiments, the metal comprises or is selected from the group consisting of Group VIB metals. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), or any combination thereof. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), vanadium (V), or any combination thereof.

[0072] In step 108, in some embodiments, the bis(first arene) metal complex is combined with a second arene.

[0073] The manner in which the bis(first arene) metal complex and the second arene are combined is not particularly limited. In some embodiments, combining comprises contacting the bis(first arene) metal complex with the second arene. In some embodiments, combining comprises mixing the bis(first arene) metal complex with the second arene. In some embodiments, combining comprises supplying the bis(first arene) metal complex and the second arene, separately or together, to a reaction vessel. In some embodiments, combining comprises flowing or feeding the bis(first arene) metal complex and the second arene, separately or together, to a reaction vessel. In some embodiments, combining comprises introducing the bis(first arene) metal complex and the second arene, separately or together, to a reaction vessel. In some embodiments, contacting comprises pouring, placing, adding, or any combination thereof, a mixture of the bis(first arene) metal complex and the second arene to a reaction vessel.

[0074] The second arene (which may be substituted or unsubstituted) may comprise a different arene from the first arene of the bis(first arene) metal complex. In some embodiments, the second arene is selected based on the first arene of the bis(first arene) metal complex. That is, the second arene may be selected to have a higher boiling point than the first arene of the bis(first arene) metal complex. For example, in some embodiments, the boiling point of the bis(first arene) is lower than the boiling point of the second arene. The second arene may be selected to have higher electron-donating properties than the first arene of the bis(first arene) metal complex. For example, in some embodiments, the first arene of the bis(first arene) metal complex may have fewer substituents (and therefore less electron-donating properties) than the second arene. Thus, in some embodiments, the second arene is selected to have a higher boiling point, a higher number of substituents (or otherwise more electron donating), or any combination thereof, relative to the arene of the bis(first arene) metal complex.

[0075] In some embodiments, the second arene is an arene of the formula: TIFF0007733839000025.tif61170[In the formula, R g , R h , R i , R j , R k , and R m are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0076] In some embodiments, the second arene is an arene of the formula: TIFF0007733839000026.tif54170[In the formula, Z is a bond, alkyl, heteroatom, or heteroalkyl; R n , R o , R p , R q , R r , R s , R t , R u , R v , and R w are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0077] In some embodiments, the second arene is a substituted arene, an unsubstituted arene, or any combination thereof. In some embodiments, the second arene is or comprises at least one substituted arene. In some embodiments, for example, the second arene comprises at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of C1-C 10Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0078] In some embodiments, for example, the second arene comprises or is selected from the group consisting of at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0079] In step 110, in some embodiments, the bis(first arene) metal complex and the second arene are heated to provide the bis(second arene) metal complex.

[0080] The manner in which the bis(first arene) metal complex and the second arene are heated is not particularly limited. In some embodiments, the heating comprises heating the bis(first arene) metal complex and the second arene to a second temperature. In some embodiments, the heating comprises heating the bis(first arene) metal complex and the second arene at a second temperature. In some embodiments, the heating comprises heating the bis(first arene) metal complex and the second arene in an oven, a furnace, or on a hot plate, or with other heating devices and / or apparatuses. In some embodiments, the heating comprises immersing the bis(first arene) metal complex and the second arene in a warm fluid bath (e.g., a hot water bath). In some embodiments, the heating comprises contacting the bis(first arene) metal complex and the second arene with a fluid (e.g., a gas or vapor, a liquid, etc.) having a second temperature. In some embodiments, the heating comprises exposing the bis(first arene) metal complex and the second arene to a fluid (eg, a gas or vapor, a liquid, etc.) having a second temperature.

[0081] In some embodiments, the second temperature is below the decomposition temperature (e.g., thermal decomposition temperature) of at least one of the bis(first arene) metal complex, the second arene, or any combination thereof. In some embodiments, the second temperature is at least the minimum reaction temperature (e.g., for ligand exchange). In some embodiments, the second temperature is in the range of 100°C to 200°C. For example, in some embodiments, the second temperature is in the range of 110°C to 200°C, 115°C to 200°C, 120°C to 200°C, 125°C to 200°C, 130°C to 200°C, 135°C to 200°C, 140°C to 200°C, 145°C to 200°C, 150°C to 200°C, 155°C to 200°C, 160°C to 200°C, 165°C to 200°C, 170°C to 200°C, 175°C to 200°C, 180°C to 200°C, 185°C to 200°C, 190°C to 200°C, 195°C to 200°C, or any combination thereof. In some embodiments, the second temperature is in the range of 100°C to 195°C, 100°C to 190°C, 100°C to 185°C, 100°C to 180°C, 100°C to 175°C, 100°C to 170°C, 100°C to 165°C, 100°C to 160°C, 100°C to 155°C, 100°C to 150°C, 100°C to 145°C, 100°C to 140°C, 100°C to 135°C, 100°C to 130°C, 100°C to 125°C, 100°C to 120°C, 100°C to 115°C, 100°C to 110°C, 100°C to 105°C, or any combination thereof.

[0082] In some embodiments, the heating is performed under vacuum. In some embodiments, the heating is performed under pressure. For example, the heating is performed at a pressure ranging from atmospheric pressure to 100 bar. In some embodiments, the pressure is in the range of at least one of 1 bar to 100 bar, 10 bar to 100 bar, 20 bar to 100 bar, 30 bar to 100 bar, 40 bar to 100 bar, 50 bar to 100 bar, 60 bar to 100 bar, 70 bar to 100 bar, 80 bar to 100 bar, 90 bar to 100 bar, 1 bar to 90 bar, 1 bar to 80 bar, 1 bar to 70 bar, 1 bar to 60 bar, 1 bar to 50 bar, 1 bar to 40 bar, 1 bar to 30 bar, 1 bar to 20 bar, 1 bar to 10 bar, 1 bar to 5 bar, or any combination thereof.

[0083] In some embodiments, the bis(secondary arene) metal complex is a compound of the formula: TIFF0007733839000027.tif34170[In the formula, M is a metal, Ar4 is the second arene]

[0084] In some embodiments, Ar4 is an arene of the formula: TIFF0007733839000028.tif61170[In the formula, R g , R h , R i , R j , R k , and R m are each independently hydrogen, halogen, dialkylamino, hydroxy, carbonyl, alkyl, alkoxy, aryl, or cycloalkyl.

[0085] In some embodiments, the bis(secondary arene) metal complex is a compound of the formula: TIFF0007733839000029.tif34170[In the formula, M is a metal, Ar5 is an arene, Ar6 is an arene, and Z is a bond, alkyl, heteroatom, or heteroalkyl.

[0086] In some embodiments, Ar5 is an arene of the formula: TIFF0007733839000030.tif54170[In the formula, R n , R o , R p , R q , R r , R s , R t , R u , R v , and R w are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0087] In some embodiments, Ar6 is an arene of the formula: TIFF0007733839000031.tif54170[In the formula, R s , R t , R u , R v , and R w are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0088] In some embodiments, the second arene is a substituted arene, an unsubstituted arene, or any combination thereof. In some embodiments, the second arene is or includes at least one substituted alkyl. In some embodiments, for example, the second arene includes at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. In some embodiments, the alkyl is a C1-C 10Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0089] In some embodiments, for example, the second arene comprises or is selected from the group consisting of at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0090] In some embodiments, the metal of the bis(secondary arene)metal complex comprises or is selected from the group consisting of transition metals. In some embodiments, the metal comprises or is selected from the group consisting of Group VIB metals. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), or any combination thereof. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), vanadium (V), or any combination thereof.

[0091] In some embodiments, the bis(secondary arene)metal complex is obtained by filtration, sublimation, distillation, or any combination thereof.

[0092] Some embodiments relate to intermediate precursors. In some embodiments, the intermediate precursors are useful for producing precursors useful for deposition processes in semiconductor fabrication processes, microelectronic fabrication processes, and the like. The intermediate precursors can be produced according to the methods disclosed herein. In some embodiments, the intermediate precursors are bis(primary arene)metal complexes disclosed herein.

[0093] In some embodiments, the intermediate precursor is a compound of the formula: TIFF0007733839000032.tif34170[In the formula, M is a metal, Ar3 is the first arene].

[0094] In some embodiments, for example, Ar3 is an arene of the formula: TIFF0007733839000033.tif61170[In the formula, R a , R b , R c , R d , R e , and R f are each independently hydrogen, halogen, dialkylamino, hydroxy, carbonyl, alkyl, alkoxy, aryl, or cycloalkyl.

[0095] In some embodiments, the first arene is a substituted arene, an unsubstituted arene, or any combination thereof. In some embodiments, the first arene is or includes at least one substituted alkyl. In some embodiments, for example, the first arene includes at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. In some embodiments, the alkyl is a C1-C 10Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0096] In some embodiments, for example, the first arene comprises or is selected from the group consisting of at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0097] In some embodiments, the metal of the bis(first arene)metal complex comprises or is selected from the group consisting of transition metals. In some embodiments, the metal comprises or is selected from the group consisting of Group VIB metals. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), or any combination thereof. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), vanadium (V), or any combination thereof.

[0098] In some embodiments, the intermediate precursor is a solid. In some embodiments, the intermediate precursor is a liquid.

[0099] In some embodiments, the intermediate precursor has a purity of 90% to 100% (i.e., pure). For example, in some embodiments, the purity of the precursor is 91% to 100%, 92% to 100%, 93% to 100%, 94% to 100%, 95% to 100%, 96% to 100%, 97% to 100%, 98% to 100%, 99% to 100%, 99.9% to 100%, 99.99% to 100%, 99.999% to 100%, 99.9999% to 100%, or 99.99999% to 100%.

[0100] Some embodiments relate to precursors. In some embodiments, the precursors are useful for deposition processes in semiconductor fabrication processes, microelectronic fabrication processes, and the like. The precursors can be made according to the methods disclosed herein. In some embodiments, the precursors are bis(secondary arene)metal complexes disclosed herein.

[0101] In some embodiments, the precursor is a compound of the formula: TIFF0007733839000034.tif34170[In the formula, M is a metal, Ar4 is the second arene].

[0102] In some embodiments, Ar4 is an arene of the formula: TIFF0007733839000035.tif61170[In the formula, R g , R h , R i , R j , R k , and R m are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0103] In some embodiments, the precursor is a compound of the formula: TIFF0007733839000036.tif34170[In the formula, M is a metal, Ar5 is an arene, Ar6 is an arene, and Z is a bond, alkyl, heteroatom, or heteroalkyl.

[0104] In some embodiments, Ar5 is an arene of the formula: TIFF0007733839000037.tif54170[In the formula, R n , R o , R p , R q , R r , R s , R t , R u , R v , and R w are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0105] In some embodiments, Ar6 is an arene of the formula: TIFF0007733839000038.tif54170[In the formula, R s , R t , R u , R v , and R w are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl.

[0106] In some embodiments, the second arene is a substituted arene, an unsubstituted arene, or any combination thereof. In some embodiments, the second arene is or includes at least one substituted alkyl. In some embodiments, for example, the second arene includes at least one of a monoalkylbenzene, a dialkylbenzene, a trialkylbenzene, a tetraalkylbenzene, or any combination thereof. In some embodiments, the alkyl is a C1-C 10Alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C2-C 10 Alkyl, C3-C 10 Alkyl, C4-C 10 Alkyl, C5-C 10 Alkyl, C6-C 10 Alkyl, C7-C 10 Alkyl, C8-C 10 In some embodiments, the alkyl is selected from the group consisting of at least one of: alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C3-C5 alkyl, or any combination thereof. In some embodiments, the alkyl is selected from the group consisting of at least one of: methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, or any combination thereof.

[0107] In some embodiments, for example, the second arene comprises or is selected from the group consisting of at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, ot-butyltoluene, mt-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, isobutylbenzene, 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.

[0108] In some embodiments, the metal of the bis(secondary arene)metal complex comprises or is selected from the group consisting of transition metals. In some embodiments, the metal comprises or is selected from the group consisting of Group VIB metals. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), or any combination thereof. In some embodiments, the metal comprises or is selected from the group consisting of at least one of chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), vanadium (V), or any combination thereof.

[0109] In some embodiments, the precursor is a solid. In some embodiments, the precursor is a liquid.

[0110] In some embodiments, the precursor has a purity of 90% to 100% (i.e., pure). For example, in some embodiments, the precursor has a purity of 91% to 100%, 92% to 100%, 93% to 100%, 94% to 100%, 95% to 100%, 96% to 100%, 97% to 100%, 98% to 100%, 99% to 100%, 99.9% to 100%, 99.99% to 100%, 99.999% to 100%, 99.9999% to 100%, or 99.99999% to 100%.

[0111] It should be understood that changes may be made in details, particularly in the materials of construction used, as well as the shape and arrangement of parts, without departing from the scope of the present disclosure. The described specification and embodiments are exemplary, with the true scope and spirit of the present disclosure being indicated by the following claims.

[0112] Example 1 Intermediate precursor: bis(benzene)molybdenum A mixture containing benzeneethylbenzenemolybdenum, benzenediethylbenzenemolybdenum, ethylbenzenediethylbenzenemolybdenum (EBDEBMo), bis(ethylbenzene)molybdenum (BEBMo), and bis(diethylbenzene)molybdenum (BDEBMo) was obtained. This mixture was combined with excess benzene (42 mL) in a sealed 350 mL tube (with a Teflon screw cap). The tube was degassed and heated to 160°C for 48 hours. Upon cooling, bis(benzene)molybdenum recrystallized and precipitated from the solution (yield: approximately 60%). The dark green crystals were isolated by filtration in a glove box and washed with hexane. The crystals were then dried under reduced pressure.

[0113] Figure 2 shows a non-limiting example of a reaction scheme for producing a precursor according to some embodiments. The reaction scheme shown in Figure 2 relates to the formation of an intermediate precursor and a precursor. 1 1 H NMR spectra were collected on crystals in C6D6. Figure 3 shows the 1 H NMR spectra of isolated bis(benzene)molybdenum according to some embodiments. 1In the H NMR spectrum of Figure 3, peak 302 is observed at 4.56 ppm for Mo(C6H6)2 and peak 304 is observed at 7.16 for the remaining reactive species (e.g., C6D6, C6H6, etc.). 1 H NMR spectroscopy confirmed that the crystals were pure and consisted solely of bis(benzene)molybdenum complexes. The absence of alkyl substituents (e.g., ethylbenzene isomers) on the benzene coordinated to the molybdenum indicates that the crystals were pure and consisted solely of bis(benzene)molybdenum complexes. 1 This was confirmed by 1 H NMR spectroscopy.

[0114] Example 2 Precursor: bis(ethylbenzene)molybdenum The bis(benzene)molybdenum intermediate precursor obtained in Example 1 was combined with ethylbenzene and heated to a temperature of 160°C to obtain bis(ethylbenzene)molybdenum. The bis(ethylbenzene)molybdenum was obtained as a liquid solution. Excess benzene present in the solution was distilled off from the solution to obtain bis(ethylbenzene)molybdenum with a purity of 99% or more.

[0115] Example 3 Intermediate precursor: bis(toluene)molybdenum A mixture of benzeneethylbenzenemolybdenum, benzenediethylbenzenemolybdenum, ethylbenzenediethylbenzenemolybdenum (EBDEBMo), bis(ethylbenzene)molybdenum (BEBMo), and bis(diethylbenzene)molybdenum (BDEBMo) is obtained. This mixture is combined with excess toluene in a sealed 350 mL tube (with a Teflon screw cap). The tube is degassed and heated to 160°C for 48 hours. Upon cooling, bis(toluene)molybdenum recrystallizes and precipitates from the solution (yield: approximately 60%). The crystals are isolated by filtration in a glove box and washed with hexane. The crystals are then dried under reduced pressure. 1 A 1 H NMR spectrum is collected, which confirms that the crystals are pure bis(toluene)molybdenum and that no arenes other than toluene are present.

[0116] Example 4 Precursor: bis(ethylbenzene)molybdenum The bis(toluene)molybdenum intermediate precursor obtained from Example 3 is combined with ethylbenzene and heated to a temperature of 160°C to obtain bis(ethylbenzene)molybdenum. The bis(ethylbenzene)molybdenum is obtained as a liquid solution. The excess toluene present in the solution is distilled off from the solution to obtain bis(ethylbenzene)molybdenum with a purity of 99% or more.

[0117] Example 5 Intermediate precursor: bis(xylene)molybdenum A mixture of benzeneethylbenzenemolybdenum, benzenediethylbenzenemolybdenum, ethylbenzenediethylbenzenemolybdenum (EBDEBMo), bis(ethylbenzene)molybdenum (BEBMo), and bis(diethylbenzene)molybdenum (BDEBMo) is obtained. This mixture is combined with excess xylene in a sealed 350 mL tube (with a Teflon screw cap). The tube is degassed and heated to 160°C for 48 hours. Upon cooling, bis(xylene)molybdenum recrystallizes and precipitates from the solution (yield: approximately 60%). The crystals are isolated by filtration in a glove box and washed with hexane. The crystals are then dried under reduced pressure. 1 A 1 H NMR spectrum is collected, which confirms that the crystals are pure bis(xylene)molybdenum and that no arenes other than xylene are present.

[0118] Example 6 Precursor: bis(xylene)molybdenum The bis(xylene)molybdenum intermediate precursor obtained from Example 5 is combined with ethylbenzene and heated to a temperature of 160°C to obtain bis(ethylbenzene)molybdenum. The bis(ethylbenzene)molybdenum is obtained as a liquid solution. Excess xylene present in the solution is distilled off from the solution to obtain bis(ethylbenzene)molybdenum with a purity of 99% or greater.

[0119] Example 7 Precursor: Bis(bibenzyl)molybdenum The bis(benzene)molybdenum intermediate precursor obtained from Example 1 is combined with bibenzyl and heated to a temperature of 160°C to obtain bis(bibenzyl)molybdenum. Bis(bibenzyl)molybdenum is obtained in a liquid solution. Excess benzene present in the solution is distilled off from the solution to obtain bis(bibenzyl)molybdenum with a purity of 99% or more. The chemical structure of bis(bibenzyl)molybdenum is shown below: TIFF0007733839000039.tif41170

[0120] Example 8 Precursor: bis(diphenylmethane)molybdenum The bis(benzene)molybdenum intermediate precursor obtained from Example 1 is combined with diphenylmethane and heated to a temperature of 160°C to obtain bis(diphenylmethane)molybdenum. The bis(diphenylmethane)molybdenum is obtained in a liquid solution. The excess benzene present in the solution is distilled off from the solution to obtain bis(diphenylmethane)molybdenum with a purity of 99% or greater. The chemical structure of bis(diphenylmethane)molybdenum is shown below: TIFF0007733839000040.tif41170

Claims

1. 1. A method of making a precursor, the method comprising: combining the mixture of bis(arene) metal complexes with a first arene; heating the mixture of the bis(arene) metal complex and the first arene; and cooling the mixture of the bis(arene) metal complex and the first arene to precipitate the bis(first arene) metal complex; Including, the metal of the bis(arene)metal complex is molybdenum; the mixture of bis(arene) metal complexes comprises at least one of benzeneethylbenzenemolybdenum, benzenediethylbenzenemolybdenum, ethylbenzenediethylbenzenemolybdenum (EBDEBMo), bis(ethylbenzene)molybdenum (BEBMo), bis(diethylbenzene)molybdenum (BDEBMo), or any combination thereof; method.

2. 2. The method of claim 1, wherein the boiling point of the arene of the bis(arene) metal complex is higher than the boiling point of the first arene.

3. 10. The method of claim 1, wherein each of the bis(arene) metal complexes present in the mixture of bis(arene) metal complexes is independently a bis(arene) metal complex of the formula: [In the formula, M is Mo; Ar １ is an arene of the formula: (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , and R ６ are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. and Ar ２ is an arene of the formula: (In the formula, R ７ , R ８ , R ９ , R １０ , R １１ , and R １２ are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. is.

4. The first arene is an arene of the formula: [In the formula, R ａ , R ｂ , R ｃ , R ｄ , R ｅ , and R ｆ are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. The method of claim 1, wherein

5. 1. A method of making a precursor, the method comprising: combining a first arene with a mixture of bis(arene) metal complexes; heating a mixture of the first arene and the bis(arene)metal complex; cooling the mixture of the first arene and the bis(arene) metal complex to obtain the bis(first arene) metal complex; combining a bis(first arene) metal complex with a second arene; and Heating the bis(first arene) metal complex and the second arene to obtain the bis(second arene) metal complex. Including, the metal of the bis(arene)metal complex is molybdenum; method.

6. The second arene has the formula: [In the formula, R ｇ , R ｈ , R ｉ , R ｊ , R ｋ , and R ｍ are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl; or [In the formula, Z is a bond, alkyl, heteroatom, or heteroalkyl; and R ｎ , R ｏ , R ｐ , R ｑ , R ｒ , R ｓ , R ｔ , R ｕ , R ｖ , and R ｗ are each independently hydrogen, halogen, dialkylamino, alkyl, alkoxy, aryl, or cycloalkyl. The method of claim 5, wherein the arene has at least one of:

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