# US 2013/0158281 A1 · Non-precious Metal-based Hyrdosilylation Catalysts Exhibiting Improved Selectivity

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- Number: US 2013/0158281 A1
- Document ID: US20130158281A1
- Status: Published application
- Kind: A1
- Application number: 13/325,250
- Filed: 2011-12-14
- Published: 2013-06-20
- Earliest claimed: 2011-12-14
- Assignees: Princeton University; Momentive Performance Materials Inc.
- Inventors: Keith James Weller; Crisita Carmen H. Atienza; Julie Boyer; Paul Chirik; Johannes G.P. Delis; Kenrick Lewis; Susan A. Nye
- Web page: https://patentgrep.com/patent/US20130158281A1

## CPC

- B01J 31/1805: {the ligands containing nitrogen}
- B01J 2231/323: Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
- B01J 2531/0244: Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
- B01J 2531/72: Manganese
- B01J 2531/842: Iron
- B01J 2531/845: Cobalt
- B01J 2531/847: Nickel
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Disclosed herein is the use of manganese, iron, cobalt, or nickel complexes containing tridentate pyridine di-imine ligands as hydrosilylation catalysts. These complexes are effective for efficiently catalyzing hydrosilylation reactions, as well as offering improved selectivity and yield over existing catalyst systems.

## Claims

### Claim 1

A process for the hydrosilylation of a composition containing a silyl hydride and a compound containing at least one unsaturated group, the process comprising: (i) contacting the composition with a complex of Formula (I), optionally in the presence of a solvent, to cause the silyl hydride to react with the compound containing at least one unsaturated group to produce a hydrosilylation product containing said complex, and (ii) optionally removing the complex from the hydrosilylation product,
wherein the complex of Formula (I) is:
wherein:
G is Mn, Fe, Ni, or Co;
x is 0 or 1;
each occurrence of R1, R2, R4, R5, R6, R7, R8 and R9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
each occurrence of R3 is independently H, C1-C18 alkyl, C1-C18 substituted alkyl, or an inert functional group, wherein R1 to R9, other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R10 optionally contains at least one heteroatom;
optionally any two of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;
wherein the silyl hydride is selected from the group consisting of R3a(R4O)bSiH (Formula II), QuTvTpHDwDHxMHyMz (Formula III), R3Si(CH2)f(SiR20)eSiR2H (Formula XX), (RO)3Si(CH2)f(SiR2O)eSiR2H (Formula XXI), and combinations thereof,
wherein Q is SiO4/2, T is R′SiO3/2, TH is HSiO3/2, D is R′2SiO2/2, DH is R′HSiO2/2, MH is HgR′3-gSiO1/2, M is R′3SiO1/2,
each occurrence of R3, R4 and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R3, R4 and R′ optionally contain at least one heteroatom;
a and b are integers 0 to 3, with the proviso that a+b=3, f has a value of 1 to 8, e has a value of 1 to 11, each g has a value of from 1 to 3, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 1000, x is from 0 to 1000, y is from 0 to 20, and z is from 0 to 20, provided that p+x+y equals 1 to 3000, and the valences of all of the elements in the silyl hydride are satisfied;
wherein the compound containing at least one unsaturated group is selected from the group consisting of an alkyne, a C2-C18 olefin, a cycloalkene, an unsaturated cycloalkane, an unsaturated cycloalkene, an unsaturated cycloalkyl epoxide, an unsaturated alkyl epoxide, a terminally unsaturated amine, an unsaturated aromatic hydrocarbon, an alkyl-capped allyl polyether, an unsaturated aryl ether, a vinyl-functionalized silane, a vinyl-functionalized silicone, a terminally unsaturated acrylate or methyl acrylate, a terminally unsaturated polyurethane polymer, and combinations thereof,
with the proviso that
when the complex of Formula (I) is iron, bis(dinitrogen)[N,N′-[(2,6-pyridinediyl κN)diethylidyne]bis[2,6-bis(1-methylethyl)benzenamine-κN]]—, (SP-5-13)-coordination compound and the silyl hydride is triethylsilane, the compound containing at least one unsaturated group cannot be an alkyl-capped allyl polyether or styrene; and
when the complex of Formula (I) is iron, bis(dinitrogen)[N,N′-[(2,6-pyridinediyl κN)diethylidyne]bis[2,6-bis(1-methylethyl)benzenamine-κN]]—, (SP-5-13)-coordination compound and the silyl hydride is methylbis(trimethylsilyloxy)silane, the compound containing at least one unsaturated group cannot be an alkyl-capped allyl polyether.

### Claim 2 (depends on 1)

The process of claim 1 comprising the step of removing the complex from the hydrosilylation product by magnetic separation, filtration and/or extraction.

### Claim 3 (depends on 1)

The process of claim 1 wherein each occurrence of R10 is independently
wherein R1, R2, R4, R5, and R6 are as defined in claim 1.

### Claim 4 (depends on 1)

The process of claim 1 wherein R1 and R2 are isopropyl groups.

### Claim 5 (depends on 1)

The process of claim 1 wherein R3 is methyl.

### Claim 6 (depends on 1)

The process of claim 1 wherein G is Fe.

### Claim 7 (depends on 1)

The process of claim 1 wherein the complex is immobilized on a support.

### Claim 8 (depends on 7)

The process of claim 7 wherein the support is selected from the group consisting of carbon, silica, alumina, MgCl2, zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), dendrimers, and combinations thereof.

### Claim 9 (depends on 8)

The complex of claim 8 wherein at least one of R1, R2, R3, R4, R5, R6, R7, R8, R9 contains a functional group that covalently bonds with the support.

### Claim 10 (depends on 1)

The process of claim 1, wherein each of p, u, v, y, and z is independently from 0 to 10, w and x are independently from 0 to 100, wherein p+x+y equals 1 to 100.

### Claim 11 (depends on 1)

The process of claim 1 wherein the silyl hydride has a structure of
wherein in Formula (IV) and Formula (V), each of R7, R8, and R9 is independently a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, R6 is hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, and x and w are independently greater than or equal to 0.

### Claim 12 (depends on 1)

The process of claim 1 wherein the silyl hydride is selected from the group consisting of (CH3O)3SiH, (C2HSO)3SiH, (CH3)3SiOSi(CH3)2H, [(CH3)3SiO]2SiH(CH3), [(CH3)2SiO]3OSiH(CH3) and [(CH3)2SiO]4OSiH(CH3).

### Claim 13 (depends on 1)

The process of claim 1 wherein the compound containing at least one unsaturated group is selected from the group consisting of R3aSiR124-a (Formula XVII), QuTvTpviDwDvixMviyMz (Formula XVIII), and combinations thereof,
wherein Q is SiO4/2, T is R′SiO3/2, R12SiO3/2, D is R′2SiO2/2Dvi is R′R12O2/2, Mvi is R12gR′3-gSiO1/2, M is R′3SiO1/2;
R12 is vinyl;
each occurrence of R3 and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R3 and R′ optionally contain at least one heteroatom;
a has a value of from 1 to 3, each g has a value of from 1 to 3, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 5000, x is from 0 to 5000, y is from 0 to 20, and z is from 0 to 20, provided that v+p+w+x+y equals 1 to 10,000, and the valences of all of the elements in the compound containing at least one unsaturated group are satisfied.

### Claim 14 (depends on 1)

The process of claim 1 wherein the compound containing at least one unsaturated group is selected from the group consisting of 1-octene, trivinyl cyclohexane, styrene, alkyl-capped allyl polyether, N,N-dimethylallylamine, a vinyl siloxane of the Formula (VI), and combinations thereof,
wherein Formula (VI) is
wherein each occurrence of R11 is independently a C1-C18 alkyl, C1-C18 substituted alkyl, vinyl, aryl, or a substituted aryl, and n is greater than or equal to zero.

### Claim 15 (depends on 1)

A composition produced from the process of claim 1 wherein the compound containing an unsaturated group is a terminally unsaturated amine, and wherein the composition is essentially free of unreacted terminally unsaturated amine and isomerization products, wherein the product is essentially free of internal addition products, and wherein the composition contains the complex of Formula (I).

### Claim 16 (depends on 1)

A composition produced from the process of claim 1 wherein the compound containing at least one unsaturated group is a vinyl-functional silicone, and wherein the composition contains the complex of Formula (I).

### Claim 17

A process for selectively producing a mono-hydrosilylated product from a composition containing a silyl hydride and a polyunsaturated compound comprising contacting the composition with a complex of Formula (I) or Formula (XIX) to cause the silyl hydride to react with the polyunsaturated compound such that hydrosilylation occurs selectively at one unsaturated group of the unsaturated compound thereby producing the mono-hydrosilylated product,
wherein Formula (I) and Formula (XIX) are:
wherein:
G is Mn, Fe, Ni, or Co;
x is 0 or 1;
each occurrence of R1, R2, R4, R5, R6, R7, R8 and R9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
each occurrence of R3 is independently H, C1-C18 alkyl, C1-C18 substituted alkyl, or an inert functional group, wherein R1 to R9, other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R10 optionally contains at least one heteroatom;
each occurrence of R15 is aryl or substituted aryl;
optionally any two of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;
wherein the polyunsaturated compound is represented by Formula (VII) or Formula (VIII)
E1[(CH2)βCR1═CH2]α, (Formula VII)
R2γE2[(CH2)βCR1═CH2]α, (Formula VIII)
wherein
E1 is a divalent or polyvalent aliphatic or aromatic cyclic hydrocarbon group containing from 3 to 25 carbon atoms, or a divalent or polyvalent aliphatic or aromatic heterocyclic hydrocarbon containing from 3 to 25 carbon atoms, wherein the heteroatom is selected from the group consisting of oxygen, nitrogen, silicon and sulfur;
E2 is a divalent or polyvalent cyclic silicone group containing from 3 to 8 silicon atoms and from 3 to 8 oxygen atoms;
each occurrence of R1 and R2 is independently a hydrogen or a hydrocarbon group containing from 1 to 8 carbon atoms;
each occurrence of α, β and γ is independently an integer, wherein α is 2 to 6; β is 0 to 6; and γ is 0 to 4;
wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the unsaturated compound is between about (0.5/α) and about (1.1/α).

### Claim 18 (depends on 17)

The process of claim 17 wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the unsaturated compound is about 1/α.

### Claim 19 (depends on 17)

The process of claim 17 wherein the unsaturated compound is selected from the group consisting of trivinylcyclohexanes, tetravinylcyclobutane, trivinyltrimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, triallylcyanurate, and triallylisocyanurate.

### Claim 20 (depends on 17)

The process of claim 17 wherein the unsaturated compound is trivinylcyclohexane.

### Claim 21 (depends on 17)

The process of claim 17 wherein the silyl hydride has one of the following structures:
wherein R3, R4, R7, R8, and R9 is each independently a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, R6 is hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, x and w are independently greater than or equal to 0, a and b are integers 0 to 3, with the proviso that a+b=3, and x is greater than or equal to 0.

### Claim 22 (depends on 17)

The process of claim 17 wherein the silyl hydride is selected from the group consisting of (CH3O)3SiH, (C2HSO)3SiH, (CH3)3SiOSi(CH3)2H, [(CH3)3SiO]2SiH(CH3), [(CH3)2SiO]3OSiH(CH3) and [(CH3)2SiO]4OSiH(CH3).

### Claim 23 (depends on 17)

The process of claim 17 wherein each occurrence of R10 is independently
wherein R1, R2, R4, R5, and R6 are as defined in claim 17.

### Claim 24 (depends on 17)

The process of claim 17 wherein the complex is immobilized on a support.

### Claim 25 (depends on 17)

A composition produced from the process of claim 17 comprising a mono-hydrosilylated product and a bis-hydrosilylated product wherein the gravimetric ratio of the mono-hydrosilylated product to the bishydrosilylated product is greater than about 1.8, and wherein the composition contains the complex of Formula (I).

### Claim 26 (depends on 25)

The composition of claim 25 wherein the gravimetric ratio of mono-hydrosilylated products to the bis-hydrosilylated products is greater than about 3.

### Claim 27 (depends on 25)

The composition of claim 25 wherein the gravimetric ratio of mono-hydrosilylated products to the bis-hydrosilylated products is greater than about 4.

### Claim 28 (depends on 25)

The composition of claim 25 containing a monosilylated divinylcyclohexane having the following general Formulae:
(H2C═CH)2C6H9CH2CH2—Si(OR)3 FORMULA IX:
(H2C═CH)2C6H9CH2CH2—SiR3 FORMULA X:
(H2C═CH)2C6H9CH2CH2—Y FORMULA XI:
wherein each occurrence of R is independently a C1-C20 alkyl, C3-C20 aliphatic or aromatic cyclic hydrocarbon group, Y is a univalent siloxanyl radical of general Formulae (XII), (XIII), or (XIV)
wherein each occurrence of R is independently a C1-C20 alkyl, C3-C20 aliphatic or aromatic cyclic hydrocarbon group, and x is greater than or equal to zero

### Claim 29

A process for selectively producing a mono-hydrosilylated product from 1,2,4-trivinylcyclohexane and a silyl hydride comprising reacting the trivinylcyclohexane with the silyl hydride in the presence of a complex of Formula (I) or Formula (XIX),
wherein Formula (I) and Formula (XIX) are:
wherein:
G is Mn, Fe, Ni, or Co;
x is 0 or 1;
each occurrence of R1, R2, R4, R5, R6, R7, R8 and R9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
each occurrence of R3 is independently H, C1-C18 alkyl, C1-C18 substituted alkyl, or an inert functional group, wherein R1 to R9, other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R10 optionally contains at least one heteroatom;
each occurrence of R15 is aryl or substituted aryl;
optionally any two of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;
wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the 1,2,4-trivinylcyclohexane is between about (0.5/3) and about (1.1/3); and
wherein the silyl group from the silyl hydride is selectively added to the 4 position of the 1,2,4-trivinylcyclohexane.

### Claim 30 (depends on 29)

The process of claim 29 wherein the silyl hydride is triethoxysilane.

### Claim 31 (depends on 29)

The process of claim 29 wherein the silyl hydride is bis(trimethylsiloxy)methylsilane.

### Claim 32 (depends on 29)

The process of claim 29 wherein the trivinylcyclohexane is a mixture of trivinylcyclohexane stereoisomers.

### Claim 33 (depends on 29)

The process of claim 29 wherein the trivinylcyclohexane is trivinylcyclohexane isomer A and/or trivinylcyclohexane isomer B, wherein isomer A and isomer B have structure Formulae (XV) and (XVI):

### Claim 34

A process for the hydrosilylation of a composition containing a silyl hydride and a compound containing at least one unsaturated group, the process comprising: (i) contacting the composition with a complex of Formula (XIX), optionally in the presence of a solvent, to cause the silyl hydride to react with the compound containing at least one unsaturated group to produce a hydrosilylation product containing said complex, and (ii) optionally removing the complex from the hydrosilylation product,
wherein the complex of Formula (XIX) is:
wherein:
G is Mn, Fe, Ni, or Co;
x is 0 or 1;
each occurrence of R1, R2, R4, R5, R6, R7, R8 and R9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
each occurrence of R15 is aryl or substituted aryl;
R1, R2, R4, R5, R6, R7, R8, R9, and R15, other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R10 optionally contains at least one heteroatom;
optionally any two of R1, R2, R15, R4, R5, R6, R7, R8, R9 and R10 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;
wherein the silyl hydride is (R4O)3SiH (Formula XXII), each occurrence of R4 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, and R4 optionally contains at least one heteroatom;
wherein the compound containing at least one unsaturated group is selected from the group consisting of a terminally unsaturated amine, an unsaturated aromatic hydrocarbon, an unsaturated cycloalkane, and combinations thereof.