Patent Application
20240109927
The present disclosure relates to the synthesis and purification of bis (arene) metal complexes, as well as related compositions and methods.
The synthesis and purification of organometallic compounds is presented with numerous challenges. Organometallic compounds are often produced in reaction mixtures containing mixed ligand complexes. Due to similar molecular weights, these organometallic compounds cannot be easily separated and purified. Organometallic compounds are also often produced in low yields. This presents issues with scaling up processes for commercial production.
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, so as 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, so as to form a reaction mixture comprising a bis (arene) metal complex; and obtaining a product.
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, so as 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, so as to form a reaction mixture comprising a bis (arene) metal complex; and contacting the reaction mixture comprising the bis (arene) metal complex, with a separation media, so as to obtain a product. In some embodiments, the product comprises a purified bis (arene) metal complex and less than 10% impurities.
Some embodiments of the present disclosure relate 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, so as 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, so as to form a reaction mixture comprising a bis (arene) metal complex.
In some embodiments of the present disclosure relates 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, so as 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, so as to form a reaction mixture comprising a bis (arene) metal complex; performing a post synthesis aqueous extraction to purify the reaction mixture and obtain product.
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 (arene) metal complex and at least one impurity; and contacting the reaction mixture comprising the bis (arene) metal complex, with a separation media, so as to obtain a product. In some embodiments, the product comprises a purified bis (arene) metal complex. In some embodiments, the product comprises less of the at least one impurity on a weight basis than the reaction mixture comprising the bis (arene) metal complex.
Some embodiments of the present disclosure relate to a composition that comprises a bis (arene) metal complex of the following formula:
where: M is Mo, Wo, or Cr; R1, R2, R3, R4, R5, and R6 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or an aryl; wherein two of R1, R2, R3, R4, R5, and R6 are optionally bonded to form a 6-membered aryl; R7, R8, R9, R10, R11, and R12 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or an aryl; wherein two of R7, R8, R9, R10, R11, and R12 are optionally bonded to form a 6-membered aryl.
Some embodiments of the disclosure are herein described, by way of example only, with reference to the accompanying drawings. With specific reference now to the drawings in detail, it is stressed that the embodiments shown are by way of example and for purposes of illustrative discussion of embodiments of the disclosure. In this regard, the description taken with the drawings makes apparent to those skilled in the art how embodiments of the disclosure may be practiced.
Among those benefits and improvements that have been disclosed, other objects and advantages of this disclosure will become apparent from the following description taken in conjunction with the accompanying figures. Detailed embodiments of the present disclosure are disclosed herein; however, it is to be understood that the disclosed embodiments are merely illustrative of the disclosure that may be embodied in various forms. In addition, each of the examples given regarding the various embodiments of the disclosure which are intended to be illustrative, and not restrictive.
Any prior patents and publications referenced herein are incorporated by reference in their entireties.
Throughout the specification and claims, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise. The phrases “in one embodiment,” “in an embodiment,” and “in some embodiments” as used herein do not necessarily refer to the same embodiment(s), though it may. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein do not necessarily refer to a different embodiment, although it may. All embodiments of the disclosure are intended to be combinable without departing from the scope or spirit of the disclosure.
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 the specification, the meaning of “a,” “an,” and “the” include plural references. The meaning of “in” includes “in” and “on.”
As used herein, the term “alkyl” refers to a hydrocarbon chain radical having from 1 to 30 carbon atoms. The alkyl may be attached via a single bond. An alkyl having n carbon atoms may be designated as a “Cn alkyl.” For example, a “C3 alkyl” may include n-propyl and isopropyl. An alkyl having a range of carbon atoms, such as 1 to 30 carbon atoms, may be designated as a C1-C30 alkyl. 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 may comprise, consist of, or consist essentially of, or may be selected from the group consisting of, at least one of a C1-C12 alkyl, a C1-C11 alkyl, a C1-C10 alkyl, a C1-C9 alkyl, a C1-C8 alkyl, a C1-C7 alkyl, a C1-C6 alkyl, a C1-C4 alkyl, a C1-C3 alkyl, or any combination thereof. In some embodiments, the alkyl may comprise, consist of, or consist essentially of, or may be selected from the group consisting of, at least one of methyl, ethyl, n-propyl, 1-methylethyl (iso-propyl), n-butyl, iso-butyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), n-pentyl, iso-pentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, octyl, decyl, dodecyl, octadecyl, or any combination thereof.
As used herein, the term “alkenyl” refers to a hydrocarbon chain radical having from 1 to 10 carbon atoms and at least one carbon-carbon double bond. Examples of alkenyl groups include, without limitation, at least one of 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, 2-hexenyl, 3-hexenyl, 1,3-hexadienyl, 1,4-hexadienyl, 2-methylpentenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, 1,3-octadienyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1-undecenyl, oleyl, linoleyl, linolenyl, or any combination thereof.
As used herein, the term “alkynyl” refers to a hydrocarbon chain radical having from 1 to 10 carbon atoms and at least one carbon-carbon triple bond. Examples of alkynyl groups include, without limitation, at least one of ethynyl, propynyl, n-butynyl, n-pentynyl, 3-methyl-1-butynyl, n-hexynyl, methyl-pentynyl, or any combination thereof.
As used herein, the term “cycloalkyl” refers to a non-aromatic carbocyclic ring having from 3 to 8 carbon atoms in the ring. The term includes a monocyclic non-aromatic carbocyclic ring and a polycyclic non-aromatic carbocyclic ring. For example, two or more cycloalkyls may be fused, bridged, or fused and bridged to obtain the polycyclic non-aromatic carbocyclic ring. In some embodiments, the cycloalkyl comprises, consists of, or consists essentially of, or is selected from the group consisting of, at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or any combination thereof.
As used herein, the term “arene” refers to a monocyclic or polycyclic aromatic hydrocarbon compound comprising carbon and hydrogen atoms. In some embodiments, the 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. The term “monocyclic,” when used as a modifier, refers to an arene having a single aromatic ring structure. The term “polycyclic,” when used as a modifier, refers to an arene having more than one aromatic ring structure, which may be fused, bridged, spiro, or otherwise bonded ring structures. In some embodiments, the terms arene and aryl are used interchangeably.
Non-limiting examples of arenes include, without limitation, at least one of benzene, toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), t-butyltoluene (e.g., o-t-butyltoluene, m-t-butyltoluene, p-t-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., 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, and the like.
At step 102, in some embodiments, the method 100 of making the bis (arene) metal complex comprises contacting a metal halide, with a first metal component and an aluminum halide, in a first solvent, so as to form a reaction mixture comprising an intermediate complex.
In an another embodiment of the present disclosure, the method used to make bis (arene) metal complex is referred to in
Referring to the method in
The contacting may comprise at least one of, directly or indirectly, reducing, reacting, introducing, heating, or any combination thereof. In some embodiments, the contacting comprises 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 comprises 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 comprises 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 comprises reducing at least one of the metal halide, the first metal component, the aluminum halide, the first solvent, or any combination thereof.
The metal halide may comprise at least one of molybdenum (Mo), chromium (Cr), tungsten (W), or any combination thereof. In some embodiments, the metal halide comprises at least one of MoCl2, MoCl3, MoCl4, MoCl5, MoCl6, or any combination thereof. In some embodiments, the metal halide comprises at least one of CrCl2, CrCl3, or any combination thereof. In some embodiments, the metal halide comprises at least one of WCl2, WCl3, WCl4, WCl5, WCl6, or any combination thereof. In some embodiments, the metal halide comprises 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 comprises at least one of WCl2, WCl3, WCl4, 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.
The first metal component may comprise a metal in a solid form. For example, in some embodiments, the first metal component may comprise a metal in a form of a powder, a particle, or a tablet. In some embodiments, the metal of the first metal component comprises 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 comprises at least one of Al, Ga, In, Zn, Sn, any alloy thereof, or any combination thereof. In some embodiments, the first metal component comprises at least one of an aluminum powder, a magnesium powder, a zinc powder, or any combination thereof. In some embodiments, the first metal component comprises an alloy. For example, in some embodiments, the first metal component comprises an aluminum magnesium alloy powder. In some embodiments, the first metal component comprises at least one of an iron powder, a nickel powder, or any combination thereof.
The first metal component may have an average particle size. The average particle size may refer to an 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 a range of 50 nm to 100 μm. For example, in some embodiments, the first metal component has an average particle size in a range of 20 μm to 100 μm, 1 μm to 5 μm, 50 nm to 900 nm, or any combination thereof, or any range or subrange therebetween.
The aluminum halide may comprise at least one of aluminum chloride, aluminum bromide, aluminum iodide, or any combination thereof. Examples of aluminum chloride include, without limitation, at least one of AlCl2, AlCl3, hydrated forms thereof, of any combination thereof. Examples of aluminum bromide include, without limitation, at least one of AlBr2, AlBr3, hydrated forms thereof, of any combination thereof. Examples of aluminum iodide include, without limitation, at least one of AlI2, AlI3, hydrated forms thereof, or any combination thereof.
The first solvent may comprise an arene. For example, the first solvent may comprise an aromatic solvent. In some embodiments, the first solvent comprises a compound of the formula:
where:
In some embodiments, the first solvent comprises a compound of the formula:
where:
In some embodiments, the first solvent does not comprise a heteroatom. In some embodiments, the first solvent does not comprise a halide.
In some embodiments, the first solvent comprises at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, o-t-butyltoluene, m-t-butyltoluene, p-t-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene, mesitylene, pseudocumene, durene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, iso-butylbenzene, sec-butylbenzene, t-butylbenzene, hexylbenzene, styrene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, methylnaphthalene, biphenylene, dimethylnaphthalene, methylanthracene, 4,4′-dimethylbiphenyl, bibenzyl, diphenylmethane, any isomer thereof, or any combination thereof. In some embodiments, the first solvent comprises an alkyl-substituted benzene. In some embodiments, the first solvent comprises an aryl-substituted benzene. In some embodiments, the first solvent does not comprise a heteroatom (e.g., as a ring atom of the arene). In some embodiments, the first solvent does not comprise a halide substituent on the arene.
The resulting reaction mixture comprises the 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 (CI), bromide (Br), or iodide (I). In some embodiments, the intermediate complex comprises [bis (toluene) molybdenum]+[AlCl4]−.
Referring to
The contacting may comprise at least one of, indirectly or directly, reducing, reacting, heating, introducing, or any combination thereof. In some embodiments, the contacting comprises contacting at least one of the intermediate complex, the second metal component, the second solvent, the reaction mixture comprising the second solvent, or any combination thereof. In some embodiments, the contacting comprises reacting at least one of the intermediate complex, the second metal component, the second solvent, the reaction mixture comprising the second solvent, or any combination thereof. In some embodiments, the contacting comprises heating at least one of the intermediate complex, the second metal component, the second solvent, the reaction mixture comprising the second solvent, or any combination thereof. In some embodiments, the contacting comprises reducing at least one of the intermediate complex, the second metal component, the second solvent, the reaction mixture comprising the second solvent, or any combination thereof.
The contacting may proceed at a second temperature. In some embodiments, the contacting comprises reducing the intermediate complex at the second temperature. In some embodiments, the second temperature is a temperature in a range of 0° C. to 150° C. In some embodiments, the second temperature is a temperature in a range of 10° C. to 150° C., 20° C. to 150° C., 30° C. to 150° C., 40° C. to 150° C., 50° C. to 150° C., 60° C. to 150° C., 70° C. to 150° C., 80° C. to 150° C., 90° C. to 150° C., 100° C. to 150° C., 110° C. to 150° C., 120° C. to 150° C., 130° C. to 150° C., 140° C. to 150° C., 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 subrange between 0° C. to 150° C.
The second metal component may comprise a metal in a solid form. For example, in some embodiments, the second metal component may comprise a metal in a form of a powder, a particle, or a tablet. In some embodiments, the metal of the first metal component comprises 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 comprises at least one of Al, Ga, In, Zn, Sn, any alloy thereof, or any combination thereof. In some embodiments, the second metal component comprises at least one of an aluminum powder, a magnesium powder, a zinc powder, or any combination thereof. In some embodiments, the second metal component comprises an alloy. For example, in some embodiments, the second metal component comprises an aluminum magnesium alloy powder. In some embodiments, the second metal component comprises at least one of an iron powder, a nickel powder, or any combination thereof. In some embodiments, the second metal component is same as the first metal component. In some embodiments, the second metal component is different from the first metal component.
The second metal component may have an average particle size. The average particle size may refer to an 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 a range of 50 nm to 100 μm. For example, in some embodiments, the second metal component has an average particle size in a range of 20 μm to 100 μm, 1 μm to 5 μm, 50 nm to 900 nm, or any combination thereof, or any range or subrange therebetween.
The second solvent may comprise an ethereal solvent. In some embodiments, the second solvent comprises a reducing solvent. In some embodiments, the second solvent comprises a solvent having a boiling point sufficient to permit removal of the solvent, under vacuum, at temperatures less than a sublimination temperature of the bis (arene) metal complex. 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 comprises a solvent having an ether linkage. In some embodiments, the second solvent comprises at least one of tetrahydrofuran, methyl tetrahydrofuran, dimethoxyethane (DME), triglyme, diethylether, diisopropylether, dibutyl ether, cyclopentylmethyl ether, methyl tert-butyl ether (MTBE), or any combination thereof. In some embodiments, the second solvent comprises 80/20 mixture of dimethoxyethane (DME) and tetrahydrofuran (THF). In some embodiments, the second solvent may comprise a solvent for dissolving the bis (arene) metal complex. In some embodiments, for example, the second solvent comprises at least one of toluene, hexane, or any combination thereof.
The resulting reaction mixture may comprise the bis (arene) metal complex. In some embodiments, the bis (arene) metal complex is a bis (first solvent) metal complex. In some embodiments, the bis (arene) metal complex comprises a compound of the formula:
where:
In some embodiments, the bis (arene) metal complex comprises at least one of a bis (benzene) metal complex, a bis (toluene) metal complex, a bis (xylene) metal complex, a bis (butyltoluene) metal complex, a bis (ethyl methyl benzene) metal complex, a bis (ethyl methylbenzene) metal complex, a bis (isopropyl methyl benzene) metal complex, a bis (butyl methylbenzene) metal complex, a bis (mesitylene) metal complex, a bis (pseudocumene) metal complex, a bis (durene) metal complex, a bis (methylbenzene) metal complex, a bis (dimethylbenzene) metal complex, a bis (trimethylbenzene) metal complex, a bis (ethylbenzene) metal complex, a bis (1,4-diethylbenzene) metal complex, a bis (triethylbenzene) metal complex, a bis (propylbenzene) metal complex, a bis (butylbenzene) metal complex, a bis (iso-butylbenzene) metal complex, a bis (sec-butylbenzene) metal complex, a bis (t-butylbenzene) metal complex, a bis (hexylbenzene) metal complex, a bis (styrene) metal complex, a bis (naphthalene) metal complex, a bis (anthracene) metal complex, a bis (phenanthrene) metal complex, a bis (biphenyl) metal complex, a bis (terphenyl) metal complex, a bis (methylnaphthalene) metal complex, a bis (biphenylene) metal complex, a bis (dimethylnaphthalene) metal complex, a bis (methylanthracene) metal complex, a bis (4,4′-dimethylbiphenyl) metal complex, a bis (bibenzyl) metal complex, a bis (diphenylmethane) metal complex, any isomer thereof, or any combination thereof.
In some embodiments, the reaction mixture comprising the bis (arene) metal complex comprises no more than 50% by weight of at least one impurity based on a total weight of the reaction mixture comprising the bis (arene) metal complex. In some embodiments, the reaction mixture comprising the bis (arene) metal complex, comprises 0.01% to 50%, 0.01% to 45%, 0.01% to 40%, 0.01% to 35%, 0.01% to 30%, 0.01% to 25%, 0.01% to 20%, 0.01% to 15%, 0.01% to 10%, 5% to 50%, 10% to 50%, 15% to 50%, 20% to 50%, 25% to 50%, 30% to 50%, 35% to 50%, 40% to 45%, or 45% to 50% by weight of the at least one impurity based on the total weight of the reaction mixture comprising the bis (arene) metal complex. In some embodiments, the impurities comprise at least one of aluminum halide impurities, coupled aromatic impurities, polyaromatic impurities, or any combination thereof. In some embodiments, the impurities comprise at least one of an aluminum halide, a tetrahydrofuran coordinated to an aluminum halide, a coupled arene compound (e.g., a dimethylbiphenyl compound), or any combination thereof. In some embodiments, the coupled arene compound comprises a compound of the formula:
where: R13, R14, R15, R16, R17, R18, R19, R20, R21, and R22 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or an aryl.
In some embodiments, the reaction mixture comprising the bis (arene) metal complex does not comprise a compound of the formula: [MXa (second solvent)b]+[MXc]−, where: M is a metal (e.g., aluminum), X is a halide (e.g., CI, Br, I, or F), a is 1 to 10, b is 1 to 10, c is 1 to 10. In some embodiments, the reaction mixture comprising the bis (arene) metal complex does not comprise [AlCl2(THF)4]+[AlCl4]−. In some embodiments, the reaction mixture comprising the bis (arene) metal complex does not comprise a detectable level of [AlCl2(THF)4]+[AlCl4]−.
Referring to
The reaction mixture comprising the bis (arene) metal complex, may be contacted with the separation media. The contacting may include flowing the reaction mixture comprising the bis (arene) metal complex, through a column containing the separation media sufficient for the separation media to remove at least a portion of the impurities present in the reaction mixture comprising the bis (arene) 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 (arene) metal complex, so as to obtain a filtered reaction mixture; drying the reaction mixture comprising the bis (arene) metal complex, so as to obtain a dried reaction mixture; contacting the reaction mixture comprising the bis (arene) metal complex, with an extracting solvent so as to obtain an extracted reaction mixture; filtering an extract organic phase from the extracted reaction mixture; or any combination thereof. In some embodiments, the extracting solvent is an aliphatic solvent. For example, in some embodiments, the aliphatic solvent comprises at least one of hexane, pentane, or any combination thereof.
The separation media may be useful for separating (e.g., sorbing, adsorbing, absorbing, etc.) the at least one impurity from the reaction mixture comprising the bis (arene) metal complex. In some embodiments, the separation media comprises at least one of neutral alumina, acidic alumina, basic alumina, florisil, silica, or any combination thereof. In some embodiments, the separation media comprises magnesium silicate. In some embodiments, the magnesium silicate is a compound of formula MgO:XSiO2, where X is 1 to 10. In some embodiments, the magnesium silicate is hydrated and is a compound of the formula MgO:XSiO2·H2O, where X is 1 to 10.
The separation media may have an average particle size. The average particle size may refer to an average particle size of at least 50% of the separation media. In some embodiments, the separation media has an average particle size of 25 microns to 250 microns. In some embodiments, the separation media has an average particle size of 25 micron to 225 micron, 25 micron to 200 micron, 25 micron to 175 micron, 25 micron to 150 micron, 25 micron to 125 micron, 25 micron to 100 micron, 25 micron to 75 micron, 25 micron to 50 micron, 50 micron to 250 micron, 75 micron to 250 micron, 100 micron to 250 micron, 125 micron to 250 micron, 150 micron to 250 micron, 175 micron to 250 micron, 200 micron to 250 micron, 225 micron to 250 micron, or any range or subrange therebetween.
Referring to
In certain embodiments of the present disclosure, the post synthesis aqueous extraction includes methods known in relevant art. By example, one method of post aqueous extraction includes drying the reaction mixture comprising the bis (arene) metal complex from step 204, so as to obtain a dried reaction mixture; this may be partially drying the reaction mixture comprising the bis (arene) metal complex so as to obtain a partially dried reaction mixture; contacting the dried or partially dried reaction mixture comprising the bis (arene) metal complex with an extracting solvent so as to obtain an extracted reaction mixture; filtering an 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 so as to obtain an aqueous extracted reaction mixture; filtering an aqueous extracted reaction mixture so as to obtain a purified organic reaction filtrate; drying a purified organic reaction filtrate so as to obtain a purified product; or any combination thereof.
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 can be −10 to 10° C. and any variations in between,
In some embodiments of the present disclosure, the extracting solvent can be an aromatic solvent. For example, in some embodiments, the aromatic solvent comprises at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, o-t-butyltoluene, m-t-butyltoluene, p-t-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-isopropyl-4-methylbenzene, 1-t-butyl-4-methylbenzene, mesitylene, pseudocumene, durene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, 1,4-diethylbenzene, triethylbenzene, propylbenzene, butylbenzene, iso-butylbenzene, sec-butylbenzene, t-butylbenzene, hexylbenzene, or any combination thereof.
In some embodiments of the present disclosure, the extracting solvent can be an aliphatic solvent. For example, in some embodiments, the aliphatic solvent comprises at least one of hexane, pentane, heptane, octane, cyclohexane, methylcyclohexane, or any combination thereof.
In some embodiments of the present invention, after step 204 in
The product in embodiments described in this present disclosure, may comprise the purified bis (arene) metal complex and less of the at least one impurity on a weight basis than the reaction mixture comprising the bis (arene) metal complex (e.g., which was contacted with the separation media). The product may comprise no more than 10% impurities. In some embodiments, for example, the product comprises 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.
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 an undetectable level of an aluminum halide as determined by 27Al NMR spectroscopy.
In some embodiments, the impurities comprise at least one of, but not limited to, magnesium halide impurities, aryl magnesium halide impurities, aryl magnesium halide impurities coordinated by an ethereal solvent, anionic aryl molybdenum “ate” complexes, aluminum halide impurities, coupled aromatic impurities, polyaromatic impurities, or any combination thereof. In some embodiments, the impurities comprise at least one of an aluminum halide, a tetrahydrofuran coordinated to an aluminum halide, a coupled arene compound (e.g., a dimethylbiphenyl compound), a methylene bridged diarene compound, or any combination thereof. In some embodiments, the coupled arene compound comprises a compound of the formula:
where: R13, R14, R15, R16, R17, R18, R19, R20, R21, and R22 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or an aryl.
In some embodiments the impurities comprise a compound of the formula
where: R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, and R34 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or an aryl.
The presence and type of impurities, including quantity of impurities, may be measured using 1H NMR spectroscopy, 27Al NMR spectroscopy, or any combination thereof. In some embodiments, the product comprises an undetectable level of an aluminum halide as determined by 27Al NMR spectroscopy.
A two-necked round-bottom flask was charged with molybdenum pentachloride (MoCl5), anhydrous aluminum trichloride (AlCl3), and aluminum powder)(A°. Toluene was added and the mixture was stirred and heated to reflex in a hot bath at about 110° C. After 40 hours the mixture was cooled to about 40° C. and tetrahydrofuran was slowly added. The mixture was heated to reflux in a hot bath, which was heated to about 100° C., for about 15 hours, before being cooled to ambient and filtered to remove excess aluminum powder. The filtrate was washed with pentane and evaporated to dryness under vacuum (0.1 Pa). Thereafter, the residue was extracted with boiling pentane and the extract was filtered and concentrated. The solution containing the extract was passed through a column packed with neutral alumina to obtain a bis (toluene) molybdenum complex. A schematic diagram of the reaction scheme is presented in
Bis(Toluene)Molybdenum Synthesis with Solvent and Reaction Time Varied. A 100 mL round bottom flask was equipped with a PTFE coated magnetic stir egg and charged with molybdenum pentachloride (3.00 g, 10.9 mmol, 1.00 eq), aluminum trichloride (1.66 g, 12.5 mmol, 1.15 eq), −325 mesh aluminum powder (0.439 g, 16.3 mmol, 1.50 eq), toluene (29.1 g, 316 mmol, 29 eq), and dodecane (18.5 g, 109 mmol, 10 eq). The mixture was stirred for 30 minutes to allow the initial exotherm (10° C. to 20° C.) to subside and was 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 allowed to cool, and the clear brownish supernatant was decanted. To the remaining dark oily lower phase containing the intermediate [(toluene)2Mo][AlCl4] was added toluene (29 g), magnesium powder (1.58 g, 65.3 mmol, 6.00 eq), and tetrahydrofuran (25.0 g) in a dropwise fashion over about 10 minutes. The deep green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium porosity fritted funnel. The green-brown filtrates were stripped of solvent under reduced pressure (100 mtorr) and then extracted with a 100 mL aliquot and a 50 ml aliquot of boiling hexanes to give a green solution after filtration. The filtrates were concentrated under reduced pressure to give 3.90 g of a gummy green solid. The green solid was dissolved in a 50/50 mixture of toluene and hexanes and subsequently eluted through a 3 cm high, 4.5 cm diameter bed of neutral alumina, leaving behind a red-brown band on the alumina and resulting in an emerald green solution. The green product solution was concentrated to a green solid under reduced pressure resulting in 1.58 g (52%) of green product. The solid green product was then sublimed in an oil bath at 110° C. and at 300 mtorr to give 1.38 g (43%) of green crystalline product.
1H NMR (400 MHz, d6-benzene, 298K): δ 4.60 (br s, 5H), 1.86 (s, 3H) ppm. 13C {1H} NMR (100 MHz, d6-benzene, 289K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.
Bis(Toluene)Molybdenum Synthesis with Solvent and Reaction Time Varied. A 100 mL round bottom flask was equipped with a PTFE coated magnetic stir egg and charged with molybdenum pentachloride (3.00 g, 10.9 mmol, 1.00 eq), aluminum trichloride (1.66 g, 12.5 mmol, 1.15 eq), −325 mesh aluminum powder (0.439 g, 16.3 mmol, 1.50 eq), and toluene (29.1 g, 316 mmol, 29 eq). The mixture was stirred for 30 minutes to allow the initial exotherm (10° C. to 20° C.) to subside and was 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 allowed to cool and was treated with magnesium powder (1.58 g, 65.3 mmol, 6.00 eq) and tetrahydrofuran (25.0 g) in a dropwise fashion over about 10 minutes. The deep green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium porosity fritted funnel. The green-brown filtrates were stripped of solvent under reduced pressure (100 mtorr) and then extracted with a 100 mL aliquot and a 50 ml aliquot of boiling hexanes to give a green solution after filtration. The filtrates were concentrated under reduced pressure to give 3.30 g of a gummy green solid. The green solid was dissolved in a 50:50 mixture of toluene and hexane and eluted through a 3 cm high, 4.5 cm diameter bed of neutral alumina, leaving behind a red-brown band on the alumina and resulting in an emerald green solution. The green product solution was concentrated to a green solid under reduced pressure resulting in 2.00 g (52%) of green product. The solid green product was then sublimed in an oil bath at 110° C. and 300 mtorr to give 1.38 g (43%) of green crystalline product. See NMR data: 1H NMR (400 MHz, d6-benzene, 298K): δ 4.60 (br s, 5H), 1.86 (s, 3H) ppm. 13C {1H} NMR (100 MHz, d6-benzene, 289K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.
Bis(Toluene)Molybdenum Synthesis with Solvent and Reaction Time Varied. A method similar to Example 2 was performed, with the exception that the initial reflux time of the reaction step forming the [(toluene)2Mo][AlCl4] was 4 hours instead of 40 hours.
Example 2 to Example 4 relate to bis (toluene) molybdenum synthesis. In each of the Examples 2 to 4, the solvent and reaction time is varied. Table 1 below summaries the solvents and reaction times employed in each of the Examples 2 to 4.
Bis(Toluene)Molybdenum Synthesis on a 10 g scale with thermal/vacuum treatment of hexanes extract. A 250 mL round bottom flask was equipped with a PTFE coated magnetic stir egg and charged with molybdenum pentachloride (10.00 g, 36.6 mmol, 1.00 eq), aluminum trichloride (5.59 g, 42.0 mmol, 1.15 eq), −325 mesh aluminum powder (1.48 g, 54.9 mmol, 1.50 eq), and toluene (101 g, 1.10 mol, 30 eq). The mixture was stirred for 1 hour to allow the initial exotherm (15° C. to 20° C.) to subside and was 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 allowed to cool and was treated with magnesium powder (5.32 g, 219 mmol, 6.00 eq) and tetrahydrofuran (84 g) in a dropwise fashion over about 15 minutes. The deep green reaction mixture was heated to reflux for 18 hours, allowed to cool, and filtered through a medium porosity fritted funnel. The green-brown filtrates were stripped of solvent under reduced pressure (100 mtorr), extracted with 2 aliquots of 250 mL boiling hexanes, filtered hot over a medium porosity frit, and then stripped of solvent under reduced pressure. The stripped hexane extracts were then analyzed by 1H NMR which showed the presence of an impurity with resonances corresponding to coordinated tetrahydrofuran (δ 3.89 (br s, 2H), 1.35 (br s, 2H) ppm). This material was then heated under a 100 mtorr vacuum in an oil bath at 100° C. for a total of 3.5 hours. The hexanes extraction process was repeated, followed by stripping under vacuum to give 12.07 g of sticky green residue. The residue was analyzed by 1H NMR which showed the disappearance of the resonances attributed to impurity-coordinated tetrahydrofuran and was also analyzed by TGA which showed that about 46 wt % of the material (5.6 g) corresponded to the Bis (toluene) Molybdenum product. This residue was purified by vacuum sublimation in a 115° C. to 140° C. oil bath at a pressure of 100 mtorr to give two sublimate fractions: 3.77 g and 2.17 g of the expected Bis(toluene)Molybdenum product (60% overall yield). The TGA analysis of the two fractions indicated a residue of 6.3 and 7.0 percent, respectively.
Use of magnesium as a reductant for the intermediate [(toluene)2Mo][AlCl4] achieved good yields and purification by sublimination from the magnesium-reduced product was performed without sacrificing yield.
Synthesis of Bis(toluene)Molybdenum using Aluminum and Magnesium as Sequential Reductants. A 100 mL round bottom flask was equipped with a PTFE coated magnetic stir egg and charged with molybdenum pentachloride (3.00 g, 10.9 mmol, 1.00 eq), aluminum trichloride (1.66 g, 12.5 mmol, 1.15 eq), −325 mesh aluminum powder (1.17, 43.6 mmol, 4.00 eq), toluene (30.1 g, 327 mmol, 30 eq). The mixture was stirred for 1 hour to allow the initial exotherm (15° C. to 20° C.) to subside and was 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 allowed to cool and then treated with tetrahydrofuran (25.0 g) in a dropwise fashion over about 15 minutes. The deep green reaction mixture was heated to reflux for 18 hours, and a small aliquot was removed, stripped of solvent, and analyzed by 1H NMR and 27Al NMR. The 1H NMR spectrum of this material displayed a resonance corresponding to the methyl group of the toluene ligand as well as tetrahydrofuran resonances corresponding to [AlCl2(THF)4] [AlCl4], but the aromatic protons of toluene were not observed. The 27Al NMR spectrum displayed a resonance at 104.0 ppm corresponding to the [AlCl2(THF)4] [AlCl4], impurity. The reaction mixture was then treated with magnesium powder (1.58 g, 65.3 mmol, 6.00 eq), refluxed an additional 18 hours, filtered through a medium porosity fritted funnel, and stripped of volatiles under reduced pressure. The green-brown filtrates were stripped of solvent under reduced pressure (100 mtorr), heated at 100° C. for 15 minutes under vacuum, and then extracted with a 100 mL aliquot and a 50 ml aliquot of boiling hexanes to give a green solution after filtration. The green solution was stripped of solvent to give 3.24 g of a sticky green solid. This green solid was analyzed by 1H NMR and 27Al NMR which indicated the formation of the desired product without the [AlCl2(THF)4] [AlCl4], impurity present. 1H 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. 13C {1H} NMR (100 MHz, d6-benzene, 289 K): δ 89.71, 78.34, 76.08, 75.14, 21.76 ppm.
Synthesis of Bis(Toluene)Molybdenum on a 36 g scale with Aluminum as a reductant and a split batch purification comparison. A 3-neck, 1 L round bottom flask was charged with molybdenum pentachloride (36.0 g, 131 mmol, 1.00 eq), aluminum trichloride (19.9 g, 150 mmol, 1.15 eq), −325 mesh aluminum powder (14.1 g, 524 mmol, 4.00 eq), toluene (350 g, 3.80 mol, 29 eq). The flask was equipped with a mechanical stirrer setup (glass stir shaft, PTFE stirrer bearing, PTFE stir paddle) and stirred around 250 RPM. The mixture was stirred for about 30 minutes to allow the initial exotherm (5° C. to 10° C.) to subside and was 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 allowed to cool and then treated with tetrahydrofuran (302 g) slowly over approximately 2 hours. The reaction mixture was then refluxed for 18 hours, allowed to cool, and filtered through a medium porosity fritted funnel. The green-brown filtrates were stripped of solvent under reduced pressure (100 mtorr), extracted with 2 aliquots of 250 mL boiling hexanes, filtered hot over a medium porosity frit, and then stripped of solvent under reduced pressure yielding 114 g of crude material. This crude product was extracted with boiling pentane (500 mL, 4×, 2 L total) and filtered to give a green solution. The solvent was evaporated from this solution under reduced pressure to give 20.10 g (55% pentane extracted crude yield) of a green solid. This green solid was analyzed by 1H NMR and 27Al NMR which showed that the [AlCl2(THF)4] [AlCl4] impurity was present in addition to the product. The pentane extracted crude product was then split up into 6 approximately equal masses and were purified according to the methods shown in Table 2 below. As shown in Table 2, passing the bis (arene) molybdenum complexes through adsorption media was superior to recrystallization at least with respect to purity and yield of the product isolated. Sublimination of an impure product was also observed to result in lower yields and lower purity.
Independent synthesis of [AlCl2(THF)4][AlCl4]. 1.0 g of AlCl3 (7.50 mmol, 1 eq) was weighed into a clear, 40 ml scintillation vial containing a micro stir bar. 10 ml of toluene was added to the vial and the mixture agitated to dissolve the solid. The reaction mixture was heated and stirred while 1.1 g (15.0 mmol, 2 eq) of THF was added in a dropwise fashion. The reaction mixture was heated for two hours at 100° C., and the solvent was allowed to slowly evaporate to give a colorless crystalline solid which was analyzed by NMR and shown to match the dominant aluminum species generated as an impurity in the Bis(toluene)Molybdenum synthesis. See NMR data: 1H NMR (400 MHz, d6-benzene, 298 K): δ 3.58 (s, 2H), 0.88 (s, 2H) ppm. 13C {1H} NMR (100 MHz, d6-benzene, 289 K): δ 74.39, 24.67 ppm. 27Al NMR (104 MHz, d6-benzene, 289 K): δ 104.0 ppm.
Synthesis of bis(toluene)molybdenum from MoCl5 at a 50 g scale. A 3 L round bottom flask was charged with molybdenum pentachloride (50.548 g, 185 mmol, 1.0 eq), aluminum trichloride (56.176 g, 421 mmol, 2.28 eq), and aluminum powder (7.395 g, 274 mmol, 1.48 eq). The flask was charged with toluene (505 g, 5.48 mol, 29.6 eq), and the reaction mixture was stirred 1 hour at ambient temperature. The reaction mixture was stirred and heated at reflux for 24 h. The reaction mixture was allowed to cool, then chilled in an ice bath, charged with magnesium powder (31.13 g, 1.28 mol, 6.91 eq) and tetrahydrofuran (422 g) in a dropwise fashion so that the internal temperature did not exceed 25° C. The reaction was heated to reflux (˜86° C.) for 18 hours and then allowed to cool to ambient temperature. The reaction mixture was filtered over to a 2 L round bottom flask and the residual salts were washed with 300 mL of anhydrous toluene. The combined filtrates were stripped of solvent under reduced pressure to give a dark green-brown solid. The crude solid was extracted 2× with hot (50° C.) anhydrous hexanes (1224 g aliquot and 578 g aliquot), and successively filtered after each hot extraction to give a clear green product solution in hexanes. The combined filtrates from the hot hexanes washes were stripped of solvent to give 50.2 g of product. The hexanes extracted product was dissolved in a solution of 300 mL toluene and 200 ml hexanes, cooled to about 5° C. in an ice bath, and treated with 60 mL of degassed deionized water in a dropwise fashion. This resulted in the formation of a light precipitate that was filtered away using a medium porosity filter funnel. The purified filtrates were then stripped of toluene under reduced pressure to give 27.3 g of green solid that was 92% pure by 1H NMR (quantitation vs hexamethyldisiloxane internal standard). The TGA analysis of the product indicated a purity of 88% based on the residual mass. The yield of the reaction based the 1H NMR weighted purity was 49%.
Synthesis of bis(toluene)molybdenum from MoCl4 at a 50 g scale which follows the reaction scheme of
Synthesis of bis (toluene) molybdenum from molybdenum tetrachloride on a 10 g scale which follows the reaction scheme of
Aspects
Various Aspects are described below. It is to be understood that any one or more of the features recited in the following Aspect(s) can be combined with any one or more other Aspect(s).
A method comprising:
[bis(first solvent) metal]+[aluminum halide]−,
[bis (first solvent) metal]+[aluminum halide]−,
where: R13, R14, R15, R16, R17, R18, R19, R20, R21, and R22 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or an aryl and R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, and R34 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, a cycloalkyl, or an aryl; magnesium halides, aluminum halides, alkali metal halides, alkaline earth metal halides, aryl magnesium halides, aryl aluminums, aryl aluminum halides, aluminum halide tetrahydrofuran complexes, aryl magnesium halide tetrahydrofuran complexes, halogenated metal compounds, anionic aryl metal complexes with alkali metal cations, anionic aryl metal complexes with alkaline earth metal cations, oligomeric metal compounds consisting of the metal coordinated by compounds of the formulae:
It is to be understood that changes may be made in detail, especially in matters of the construction materials employed and the shape, size, and arrangement of parts without departing from the scope of the present disclosure. This Specification and the embodiments described are examples, with the true scope and spirit of the disclosure being indicated by the claims that follow.
| Number | Date | Country | |
|---|---|---|---|
| 63404825 | Sep 2022 | US |
