Granted Patent B2

US 8,236,915 · App. 12/832,627 · Granted Aug 7, 2012

Abstract

Claims (110)

1. A complex of Formula (I)

or Formula (II)

wherein:

G is Mn, Fe, Ni, or Co;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently hydrogen, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group, wherein R 2 -R 9 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 23 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 23 optionally contains at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 23 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

L 1 -L 2 is

wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, are optionally substituted,

each occurrence of R 12 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C2-C18 alkenyl, C2-C18 substituted alkenyl, C2-C18 alkynyl, C2-C18 substituted alkynyl, aryl, substituted aryl, wherein R 12 optionally contains at least one heteroatom;

optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkyl, substituted alkyl, or a heteroatom, wherein R 19 and R 20 optionally contain at least one heteroatom;

wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 ;

with the proviso that

(1) R 1 in Formula (I) is hydrogen, methyl, ethyl or n-propyl; and

(2) L 1 -L 2 of Formula (A) is selected from the group consisting of 1,5-cyclooctadienes, dicyclopentadienes, and norbornadienes.

2. A complex according to Formula (I) or Formula (II) of claim 1 wherein R 23 is

wherein R 1 , R 2 , R 4 , R 5 and R 6 are as defined in claim 1 .

3. A complex according to Formula (I) or Formula (II) of claim 1 wherein R 1 and R 2 in Formula (I) are both methyl, ethyl or n-propyl groups, and R 1 and R 2 in Formula (II) are both methyl, ethyl, n-propyl or isopropyl groups.

4. A complex according to Formula (I) or Formula (II) of claim 1 wherein R 3 is methyl.

5. A complex according to Formula (I) or Formula (II) of claim 1 wherein R 10 , R 11 , R 13 , R 14 , R 15 , and R 16 are hydrogen.

6. A complex according to Formula (II) of claim 1 being

wherein G, R 1 -R 9 , R 17 , R 18 and R 23 are as defined in claim 1 .

7. A complex according to Formula (II) of claim 1 being

wherein G, R 1 -R 9 and R 23 are as defined in claim 1 .

8. A complex according to Formula (II) of claim 1 wherein L 1 -L 2 is an organosiloxane having at least four unsaturated sites, and wherein the complex is a dimer.

9. A complex according to Formula (I) or Formula (II) of claim 1 wherein G is Fe.

10. A complex according to Formula (I) of claim 1 or Formula (II) wherein the complex is immobilized on a support, and wherein Formula (II) is

wherein:

G is Mn, Fe, Ni, or Co;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently hydrogen, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group, wherein R 2 -R 9 , other than hydrogen, optionally contain at least one heteroatom:

each occurrence of R 23 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 23 optionally contains at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 13 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

L 1 -L 2 is

wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, are optionally substituted,

each occurrence of R 12 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C2-C18 alkenyl, C2-C18 substituted alkenyl, C2-C18 alkynyl, C2-C18 substituted alkynyl, aryl, substituted aryl, wherein R 12 optionally contains at least one heteroatom;

optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkyl, substituted alkyl, or a heteroatom, wherein R 19 and R 20 optionally contain at least one heteroatom;

wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 .

11. The complex of claim 10 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.

12. The complex of claim 10 wherein at least one of R 1 -R 9 contains a functional group that covalently bonds with the support.

13. A complex according to Formula (I) of claim 1 wherein R 2 is hydrogen, methyl, ethyl or isopropyl.

14. 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 according to Formula (I) of claim 1 , or a complex of Formula (II), (III), or (IV), 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

Formula (II) is:

Formula (III) is:

wherein

G is Mn, Fe, Ni, or Co;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group, wherein R 2 -R 9 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 22 and R 23 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R 22 and R 23 optionally contain at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 23 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

L 1 -L 2 is

wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, are optionally substituted,

each occurrence of R 12 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C2-C18 alkenyl, C2-C18 substituted alkenyl, C2-C18 alkynyl, C2-C18 substituted alkynyl, aryl, substituted aryl, wherein R 12 optionally contains at least one heteroatom;

optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkyl, substituted alkyl, or a heteroatom, wherein R 19 and R 20 optionally contain at least one heteroatom;

wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 ;

L 1 is R 10 R 11 C═CR 12 R 13 or R 18 C≡CR 19 and L 2 is R 14 R 15 C═CR 16 R 17 or R 20 C≡CR 21 , wherein each occurrence of R 10 -R 21 is independently hydrogen, C1-C18 alkyl, C1-C18 alkenyl, or C1-C18 alkynyl, wherein optionally R 18 -R 19 and/or R 20 -R 21 , and/or any two of R 10 , R 11 , R 12 , R 13 and/or any two of R 14 , R 15 , R 16 R 17 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R 10 -R 21 , other than hydrogen, optionally contain at least one heteroatom, and R 10 -R 21 , other than hydrogen, are optionally substituted, and wherein L 1 and L 2 bond with G through unsaturated sites.

15. The process of claim 14 comprising the step of removing the complex from the hydrosilylation product by magnetic separation and/or filtration.

16. The process of claim 14 wherein each occurrence of R 23 is independently

wherein R 1 , R 2 , R 4 , R 5 and R 6 are as defined in claim 14 .

17. The process of claim 14 wherein R 1 and R 2 in Formula (I) are both methyl, ethyl or n-propyl groups, and R 1 and R 2 in Formula (II) are both methyl, ethyl, n-propyl or isopropyl groups.

18. The process of claim 14 wherein R 3 is methyl.

19. The process of claim 14 wherein R 10 , R 11 , R 14 , R 15 , R 18 and R 20 are hydrogen.

20. The process of claim 14 wherein the complex is

wherein G, R 1 -R 9 , R 17 , R 18 and R 23 are as defined in claim 1 .

21. The process of claim 14 wherein R 17 and R 18 are methyl groups.

22. The process of claim 14 wherein G is Fe.

23. The process of claim 14 wherein the complex is immobilized on a support.

24. The process of claim 23 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.

25. The process of claim 23 wherein at least one of R 1 -R 9 contains a functional group that covalently bonds with the support.

26. The process of claim 14 , wherein the silyl hydride is selected from the group consisting of R 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′SiO 3/2 , T H is HSiO 3/2 , D is R′ 2 SiO 2/2 , D H is R′HSiO 2/2 , M H is H g R′ 3-g 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 and R′ optionally contain at least one heteroatom, each occurrence of a independently has a value of from 1 to 3, g has a value of from 0 to 3, each of p, u, v, y and z is independently from 0 to 20, w and x are independently from 0 to 500, provided that p+x+y equals 1 to 500, and the valences of the all the elements in the silyl hydride are satisfied.

27. The process of claim 26 , 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.

28. The process of claim 14 , 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 methylallyl polyether, a terminally unsaturated amine, an alkyne, a C2-C18 olefin, an unsaturated cycloalkyl epoxide, a terminally unsaturated acrylate or methyl acrylate, an unsaturated aryl ether, an unsaturated aromatic hydrocarbon, an unsaturated cycloalkane, a vinyl-functionalized polymer, a vinyl-functionalized silane, a vinyl-functionalized silicone, and combinations thereof.

29. The process of claim 14 , wherein the compound containing an unsaturated group is a polyoxyalkylene having the generic formula:

R 1 (OCH 2 CH 2 ) z (OCH 2 CHR 3 ) w —OR 2 ,  Formula (VIII)

R 2 O(CHR 3 CH 2 O) w (CH 2 CH 2 O) z —CR 4 2 —C≡C—CR 4 2 —(OCH 2 CH 2 ) z (OCH 2 CHR 3 ) w R 2 or  (Formula X) or

H 2 C═CR 4 CH 2 O(CH 2 OCH 2 ) z (CH 2 OCHR 3 ) w CH 2 CR 4 ═CH 2   (Formula XI)

wherein each occurrence of R 1 is an unsaturated organic group containing from 2 to 10 carbon atoms, each occurrence of R 2 is independently hydrogen, vinyl, or a polyether capping group of from 1 to 8 carbon atoms, each occurrence of R 3 and R 4 are independently monovalent hydrocarbon groups, each occurrence of z is 0 to 100 inclusive, and each occurrence of w is 0 to 100 inclusive.

30. A process for preparing a silylated polyurethane comprising contacting a terminally unsaturated polyurethane polymer with a silyl hydride in the presence of a complex as defined in claim 14 .

31. A composition produced from the process of claim 14 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 from the process of claim 14 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, and wherein the product is essentially free of internal addition products.

33. A composition produced from the process of claim 14 wherein the compound containing at least one unsaturated group is a vinyl-functional silicone.

34. A process for the synthesis of a complex of Formula (I) as defined in claim 1 comprising the step of reacting a compound of Formula (V) with a reducing agent having a reduction potential more negative than −0.6 v versus ferrocene in the presence of nitrogen, wherein Formula (V) is

wherein

G is Mn, Fe, Ni, or Co;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert group, wherein R 2 -R 9 , other than hydrogen, optionally contain at least one heteroatom;

R 23 is C1-C18 alkyl group or C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R 23 optionally contains at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 23 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

X is an anion.

35. The process of claim 33 wherein the reducing agent is sodium naphthalenide.

36. The process of claim 33 wherein X is F, Cl, Br, I, CF 3 R 40 SO 3 − or R 50 COO − , wherein R 40 is a covalent bond or a C1-C6 alkyl group, and R 50 is a C1-C10 hydrocarbyl group.

37. A process for the synthesis of a complex of Formula (II) as defined in claim 1 comprising the step of reacting a complex of Formula (V) with L 1 -L 2 wherein Formula (V) is

wherein

G is Mn, Fe, Ni, or Co;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert group, wherein R 2 -R 9 , other than hydrogen, optionally contain at least one heteroatom;

R 23 is C1-C18 alkyl group or C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R 23 optionally contains at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 23 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

X is F, Cl, Br, I, CF 3 R 40 SO 3 − or R 50 COO − , wherein R 40 is a covalent bond or a C1-C6 alkyl group, and R 50 is a C1-C10 hydrocarbyl group; and

L 1 -L 2 is

wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, or aryl, wherein R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, are optionally substituted,

each occurrence of R 12 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C2-C18 alkenyl, C2-C18 substituted alkenyl, C2-C18 alkynyl, C2-C18 substituted alkynyl, aryl, or substituted aryl, wherein R 12 optionally contains at least one heteroatom;

optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together may optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkyl, substituted alkyl or an heteroatom, wherein R 19 , and R 20 optionally contain at least one heteroatom,

wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 ;

with the proviso that L 1 -L 2 of Formula (A) is selected from the group consisting of 1,5-cyclooctadienes dicyclopentadienes, and norbornadienes.

38. The process of claim 14 wherein R 2 in Formula (I) is hydrogen, methyl, ethyl or isopropyl.

Assignments (25)