NOBLE METAL-FREE HYDROSILYLATABLE MIXTURE

Abstract

The invention relates to a hydrosilylatable mixture M containing: (A) a compound with at least one hydrogen atom directly bonded to Si, (B) a compound containing at least one carbon-carbon multiple bond, and (C) a compound containing at least one cationic Si(II) group. The invention also relates to a method for hydrosilylating the mixture M.

Claims

1. A hydrosilylable mixture M comprising: (A) a compound having at least one hydrogen atom bonded directly to Si, (B) a compound comprising at least one carbon-carbon multiple bond and (C) a compound comprising at least one cationic Si(II) moiety, wherein the compound C is a cationic Si(II) compound of general formula IV
([Si(II)Cp].sup.+).sub.aX.sup.a(IV) in which Cp is p-bonded cyclopentadienyl radical of general formula V, which is substituted by radicals R.sup.y, ##STR00004## R.sup.y are monovalent radicals or polyvalent radicals, which can also bond to one another to form fused rings and X.sup. signifies an a valent anion, which does not react with the cationic silicon(II) under the reaction conditions of hydrosilylation, or compound C is selected from the cationic Si(II) compounds of the group consisting of: ##STR00005## wherein the radicals R.sup.a are each independently hydrocarbon radicals and Hal signifies halogen.

2. A method for hydrosilylating mixture M comprising: reacting a compound A with a compound B in the presence of a compound C as a hydrosilylation catalyst, wherein the compound A has at least one hydrogen atom bonded directly to Si, the compound B comprising at least one carbon-carbon multiple bond and the compound C comprising at least one cationic Si(II) moiety, wherein the compound C is a cationic Si(II) compound of general formula IV
([Si(II)Cp].sup.+).sub.aX.sup.a(IV) in which Cp is p-bonded cyclopentadienyl radical of general formula V, which is substituted by radicals R.sup.y, ##STR00006## R.sup.y are monovalent radicals or polyvalent radicals, which can also bond to one another to form fused rings and X.sup. signifies an a valent anion, which does not react with the cationic silicon(II) under the reaction conditions of hydrosilylation, or the compound C is selected from the cationic Si(II) compounds of the group consisting of: ##STR00007## wherein the radicals R.sup.a are each independently hydrocarbon radicals and Hal signifies halogen.

3. The hydrosilylable mixture M as claimed in claim 1, wherein compound A has general formula I
R.sup.1R.sup.2R.sup.3SiH(I) wherein the radicals R.sup.1, R.sup.2 and R.sup.3 each independently are hydrogen, halogen, silyloxy radical, hydrocarbon radical or hydrocarbonoxy radical, wherein individual carbon atoms in each case may be replaced by oxygen atoms, silicon atoms, nitrogen atoms, halogen, sulfur or phosphorus atoms.

4. The hydrosilylable mixture M as claimed in claim 1, wherein compound B is selected from compounds of the group consisting of general formula IIIa
R.sup.4R.sup.5CCR.sup.6R.sup.7(IIIa), and of general formula IIIb
R.sup.8CCR.sup.9(IIIb), wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently linear, branched, acyclic or cyclic, saturated or mono- or polyunsaturated C1-C20 hydrocarbon radicals, wherein individual carbon atoms may be replaced by silicon, oxygen, halogen, nitrogen, sulfur or phosphorus.

5. The hydrosilylable mixture M as claimed in claim 1, wherein R.sup.a is an unbranched alkyl radical or 2,6-dialkylated phenyl radical.

6. The hydrosilylable mixture M as claimed in claim 1, wherein the molar ratio between compound C and the SiH moieties present in compound A is from 1:10.sup.7 to 1:50.

7. The method of hydrosilylating mixture M as claimed in claim 2, wherein the compound A has general formula I
R.sup.1R.sup.2R.sup.3SiH(I) wherein the radicals R.sup.1, R.sup.2 and R.sup.3 each independently have the definition hydrogen, halogen, silyloxy radical, hydrocarbon radical or hydrocarbonoxy radical, wherein individual carbon atoms in each case may be replaced by oxygen atoms, silicon atoms, nitrogen atoms, halogen, sulfur or phosphorus atoms.

8. The method of hydrosilylating mixture M as claimed in claim 2, wherein the compound B is selected from compounds of the group consisting of general formula IIIa
R.sup.4R.sup.5CCR.sup.6R.sup.7(IIIa), and general formula IIIb
R.sup.8CCR.sup.9(IIIb), wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently linear, branched, acyclic or cyclic, saturated or mono- or polyunsaturated C1-C20 hydrocarbon radicals, wherein individual carbon atoms may be replaced by silicon, oxygen, halogen, nitrogen, sulfur or phosphorus.

9. The method of hydrosilylating mixture M as claimed in claim 2, wherein R.sup.a is an unbranched alkyl radical or 2,6-dialkylated phenyl radical.

10. The method of hydrosilylating mixture M as claimed in claim 2, wherein the molar ratio between the compound C and the SiH moieties present in the compound A is from 1:10.sup.7 to 1:50.

Description

EXAMPLE 1

[0052] Hydrosilylation of -Methylstyrene with Triethylsilane with Addition of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup.

[0053] All working steps are carried out under Ar. 120 mg (1.02 mmol) of -methylstyrene and 116 mg (1.01 mmol) of triethylsilane were each weighed into a screw-topped glass vial and 0.5 ml of CD.sub.2Cl.sub.2 was added in each case. The two solutions were mixed with each other. Then, at 20 C., a solution of 25.4 mg (0.0302 mmol, 3.0 mol %) of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. in 1 ml of CD.sub.2Cl.sub.2 was added to the mixture of -methylstyrene and triethylsilane.

[0054] After one hour, ca. 30% of triethylsilane had reacted and overnight the reaction was complete (monitoring of the reaction by NMR spectroscopy). The product phenyl-CH(CH.sub.3)CH.sub.2Si(ethyl).sub.3 was formed.

[0055] The .sup.1H-NMR signal of the catalyst (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. at =2.22 ppm was detected in unaltered amount; there was no measurable decrease.

EXAMPLE 2

[0056] Hydrosilylation of -Methylstyrene with Triethylsilane with Addition of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup.

[0057] All working steps are carried out under Ar. 236 mg (2.00 mmol) of -methylstyrene and 233 mg (2.00 mmol) of triethylsilane were each weighed into a screw-topped glass vial and 0.5 ml of CD.sub.2Cl.sub.2 was added in each case. The two solutions were mixed with each other. Then, at 20 C., a solution of 6.4 mg (0.0075 mmol, 0.38 mol %) of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. in 1 ml of CD.sub.2Cl.sub.2 was added to the mixture of -methylstyrene and triethylsilane.

[0058] After one hour, ca. 35% of triethylsilane had reacted and overnight the reaction was complete (monitoring of the reaction by NMR spectroscopy). The product phenyl-CH(CH.sub.3)CH.sub.2Si(ethyl).sub.3 was formed. The .sup.1H-NMR signal of the catalyst (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. at =2.22 ppm was detected in unaltered amount; there was no measurable decrease.

EXAMPLE 3

[0059] Hydrosilylation of -Methylstyrene with Dimethylphenylsilane with Addition of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup.

[0060] All working steps are carried out under Ar. 236 mg (2.00 mmol) of -methylstyrene and 272 mg (2.00 mmol) of dimethylphenylsilane were each weighed into a screw-topped glass vial and 0.5 ml of CD.sub.2Cl.sub.2 was added in each case. The two solutions were mixed with each other. Then, at 20 C., a solution of 25.4 mg (0.0075 mmol, 0.38 mol %) of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. in 1 ml of CD.sub.2Cl.sub.2 was added to the mixture of -methylstyrene and dimethylphenylsilane.

[0061] After one hour, >90% of dimethylphenylsilane had reacted and overnight the reaction was complete (monitoring of the reaction by NMR spectroscopy). The product phenyl-CH(CH.sub.3)CH.sub.2Si(CH.sub.3).sub.2phenyl was formed. The .sup.1H-NMR signal of the catalyst (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. at =2.20 ppm was detected in unaltered amount; there was no measurable decrease.

EXAMPLE 4

[0062] Hydrosilylation of -Methylstyrene with Pentamethyldisiloxane with Addition of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup.

[0063] All working steps are carried out under Ar. 119 mg (1.01 mmol) of -methylstyrene and 148 mg (1.00 mmol) of pentamethyldisiloxane were each weighed into a screw-topped glass vial and 0.5 ml of CD.sub.2Cl.sub.2 was added in each case. The two solutions were mixed with each other. Then, at 20 C., a solution of 1.8 mg (0.0021 mmol, 0.21 mol %) of (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5).sub.4.sup. in 1 ml of CD.sub.2Cl.sub.2 was added to the mixture of -methylstyrene and pentamethyldisiloxane.

[0064] After one hour, the reaction was complete (.sup.1H-NMR spectrum). The product phenyl-CH(CH.sub.3)CH.sub.2Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.3 was formed. The .sup.1H-NMR signal of the catalyst (-Me.sub.5C.sub.5)Si.sup.+ B(C.sub.6F.sub.5)C.sub.4.sup. at =2.20 ppm was detected in unaltered amount; there was no measurable decrease.