Activation of metal salts with silylhydrides and their use in hydrosilylation reactions
View Patent ↗The invention relates generally to transition metal salts, more specifically to iron, nickel, cobalt, manganese and ruthenium salts, activated with silylhydrides, and their use as efficient hydrosilylation catalysts.
1. A process for the hydrosilylation of an unsaturated compound comprising at least one carbon-carbon unsaturated group with a silylhydride in the presence of a metal complex of Formula (I), Formula (II), or a combination thereof:
GXn Formula (II);
wherein the process comprises activating the metal complex with a silylhydride and a promoter compound, and G is Mn, Fe, Ni, Ru, or Co; each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert group, wherein any two neighboring R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 groups taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R 1 -R 7 other than hydrogen, optionally contain at least one heteroatom; X in Formula (I) is an anion;
X in Formula (II) is an anion or an oxygen atom, and n=1-3 including non-integers, and wherein the promoter compound is an organic compound that is other than a reducing agent.
2. The process of claim 1 , wherein a single silylhydride is employed for activating the metal complex and for the hydrosilylation reaction.
3. The process of claim 2 , wherein the silylhydride is chosen from phenylsilane.
4. The process of claim 2 , wherein the silylhydride is triethoxysilane.
5. The process of claim 1 , wherein the silylhydride employed to activate the metal complex is different than the silylhydride undergoing hydrosilylation with the unsaturated compound.
6. The process of claim 5 , wherein the silylhydride employed to activate the metal complex is chosen from phenylsilane and triethoxysilane, and the silylhydride undergoing hydrosilylating the unsaturated compound is chosen from R 10 a SiH 4-a , (RO) a SiH 4-a , Q u T v T p H D w D H x M H y M z , and combinations thereof, wherein Q is SiO 4/2 , T is R 4 SiO 3/2 , T H is HSiO 3/2 , D is R 11 2 SiO 2/2 , D H is R 11 HSiO 2/2 , M H is HR 11 2 SiO 1/2 , M is R′ 3 SiO 1/2 , each occurrence of R and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R 10 and R 11 optionally contain at least one heteroatom, each occurrence of a independently has a value 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 the all the elements in the silylhydride are satisfied.
7. The process of claim 1 wherein the promoter has a pKb greater than 9.7.
8. The process of claim 1 wherein the promoter is selected from the group consisting of pyridine(di)imine type compounds, 2,6-dimethanolpyridine, 2,6-diacetylpyridine, tetramethylethylenediamine (TMEDA), tetrabutylammonium fluoride (TBAF), NaOAc, Liacac, and N and O containing ligands, or combinations of two or more thereof.
9. The process of claim 1 wherein the promoter is Mes PDI ((2,4,6Me 3 C 6 H 2 N═CMe) 2 (C 5 H 3 N)).
10. The process of claim 1 , wherein Formula (I) is Mes PDIFeCl 2 ((2,4,6Me 3 C 6 H 2 N═CMe) 2 (C 5 H 3 N)FeCl 2 ).
11. The process of claim 1 , wherein X in Formula (I) or Formula (II) is chosen from F − , Cl − , Br − , I − , an enolate, an acetylacetonate, CF 3 R 8 SO 3 − or R 9 COO − , wherein R 8 is a covalent bond or a C1-C6 alkylene group, and R 9 is a C1-C10 substituted or unsubstituted hydrocarbyl group, optionally containing at least one heteroatom.
12. The process of claim 1 , wherein the unsaturated organic substrate contains an internal olefin.
13. The process of claim 12 , wherein said process produces an internal addition product.
14. The process of claim 13 , wherein said internal addition product is converted into an internal alcohol.
15. The process of claim 1 , wherein said process produces an internal addition product.
16. The process of claim 15 , wherein said internal addition product is converted into an internal alcohol.
17. The process of claim 1 , wherein the complex according to Formula (I) is immobilized on a support.
18. The process of claim 17 , wherein the support is selected from the group consisting of carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), dendrimers, and combinations thereof.
19. The process of claim 18 , wherein at least one of R 1 -R 7 contains a functional group that covalently bonds with the support.
20. The process of claim 1 , wherein the silylhydride for hydrosilylating the unsaturated compound is selected from the group consisting of R 10 a SiH 4-a , (RO) a SiH 4-a , Q u T v T p H D w D H x M H y M z , and combinations of two or more thereof, wherein Q is SiO 4/2 , T is R 4 SiO 3/2 , T H is HSiO 3/2 , D is R 11 2 SiO 2/2 D H is R 11 HSiO 2/2 , M H is HR 11 2 SiO 1/2 , M is R′ 3 SiO 1/2 , each occurrence of R and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R 10 and R 11 optionally contain at least one heteroatom, each occurrence of a independently has a value 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 the all the elements in the silylhydride are satisfied.
21. The process of claim 20 , wherein p, u, v, y, and z are from 0 to 10, w and x are from 0 to 100, wherein p+x+y equals 1 to 100.
22. The process of claim 1 , wherein the compound containing an unsaturated group is selected from the group consisting of an alkyl-capped allyl polyether, a vinyl functionalized alkyl-capped allyl or methallyl polyether, a terminally unsaturated amine, an alkyne, a C2-C40 olefin, an unsaturated alkyl or cycloalkyl epoxide, a terminally unsaturated acrylate or methyl acrylate, an unsaturated aryl ether, an aralkene or aralkyne, an unsaturated cycloalkane, an internal olefin, an unsaturated acid or ester, a vinyl-functionalized polymer or oligomer, an alkenyl-functional silane, an alkenyl-functional silicone, a vinyl-functionalized silane, a vinyl-functionalized silicone, and combinations thereof.
23. The process of claim 1 , wherein the compound containing an unsaturated group is a polyoxyalkylene having the generic formula:
R 12 (OCH 2 CH 2 ) z (OCH 2 CHR 14 ) w —OR 13 (Formula III),
R 13 O(CHR 14 CH 2 O) w (CH 2 CH 2 O) z —CR 15 2 —C≡C—C 15 2 —(OCH 2 CH 2 ) z (OCH 2 CHR 14 ) w R 16 (Formula IV) or
H 2 C═CR 15 CH 2 O(CH 2 CH 2 O) z (CH 2 CHR 14 O) w CH 2 CR 15 ═CH 2 (Formula V)
wherein each occurrence of R 12 is an unsaturated organic group containing from 2 to 10 carbon atoms, each occurrence of R 13 is independently hydrogen, vinyl, or a polyether capping group of from 1 to 8 carbon atoms, each occurrence of R 14 and R 15 are independently monovalent hydrocarbon groups, except that R 15 can also be chosen from hydrogen each occurrence of R 16 is vinyl, or a polyether capping group of from 1 to 8 carbon atoms, each occurrence of z is 0 to 100 inclusive, and each occurrence of w is 0 to 100 inclusive.
24. The process of claim 1 wherein the reaction is carried out at a temperature of −40 C to 200 C.
25. The process of claim 1 wherein the reaction is conducted under an inert atmosphere.
26. The process of claim 1 wherein the reaction is conducted neat or in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combination thereof.
27. The process of claim 1 , wherein Formula (II) is iron stearate.
28. The process of claim 1 , wherein Formula (II) is an iron oxide.
29. The process of claim 1 further comprising removing the complex and or derivatives thereof from the hydrosilylated product.
30. A composition produced by a process according to claim 1 , wherein the composition contains the catalyst and/or derivatives thereof.
31. A composition produced by the process of claim 1 , wherein the compound containing an unsaturated group is an alkyl-capped allyl polyether; and wherein the composition is essentially free of unreacted alkyl-capped allyl polyether and its isomerization products.
32. A composition produced by the process of claim 1 , wherein the compound containing at least one unsaturated group is a vinyl-functionalized silicone.
33. The process of claim 1 , wherein the silylhydride, unsaturated compound, promoter, and metal complex are provided in one solution.
34. The process of claim 1 comprising adding a solution comprising the silylhydride, the unsaturated compound, and the promoter to a solution comprising the metal complex.
35. The process of claim 1 comprising (a) providing a solution comprising the metal complex and the promoter, and (b) adding a solution comprising the silylhydride and the unsaturated compound to the solution of (a).
36. A process for the hydrosilylation of a composition containing a silylhydride and a compound containing at least one unsaturated group, the process comprising:
reacting a substrate silylhydride with a compound containing at least one carbon-carbon unsaturated group in the presence of an activating silylhydride, a promoter compound, and a metal complex to produce a hydrosilylation product containing said complex and/or derivatives thereof,
wherein the metal complex is chosen from a complex of Formula (I), Formula (II), or a combination thereof; where Formula (I) is:
Formula (II) is: GXn; G is Mn, Fe, Ni, Ru, or Co; each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R 1 -R 7 other than hydrogen, optionally contain at least one heteroatom; X in Formula (I) is an anion; X in Formula (II) is an anion or an oxygen atom, and n=1-3 including non-integers, and wherein the promoter compound is an organic compound that is other than a reducing agent.
37. The process of claim 36 , wherein the substrate silylhydride is also the activating silylhydride and can be added as a single material.
38. The process of claim 37 , wherein the substrate silylhydride is phenylsilane.
39. The process of claim 37 , wherein the substrate silylhydride is triethoxysilane.
40. The process of claim 36 , wherein substrate silylhydride is different from the activating silylhydride.
41. The process of claim 36 , wherein the activating silylhydride is phenylsilane.
42. The process of claim 36 , wherein the activating silylhydride is triethoxysilane.
43. The process of claim 36 , wherein the reacting step comprises (a) providing a mixture of the metal complex, the promoter, and the activating silylhydride, (b) providing a mixture of the substrate silylhydride and the unsaturated compound, and adding (b) to (a).
44. The process of claim 36 , wherein the reacting step comprises (a) providing a mixture of the metal complex, the unsaturated compound, the promoter, and the activating silylhydride, (b) providing a composition comprising the substrate silylhydride, and adding (b) to (a).
45. The process of claim 36 , wherein the reacting step comprises (a) providing a mixture of the metal complex, the substrate silylhydride, the promoter, and the activating silylhydride, (b) providing a composition comprising the unsaturated compound, and adding (b) to (a).
46. The process of claim 1 having a molar ratio of the promoter to the metal complex of from 1000:1 to 1:1.
47. The process of claim 1 having a molar ratio of the promoter to the metal complex of from 10:1 to 1:1.
48. The process of claim 36 having a molar ratio of the promoter to the metal complex of from 1000:1 to 1:1.
49. The process of claim 36 having a molar ratio of the promoter to the metal complex of from 10:1 to 1:1.