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 hydrosilylatable 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 formula IV
([Si(II)Cp].sup.+).sub.aX.sup.a(IV) in which Cp is a -bonded cyclopentadienyl radical of formula V, which is substituted by radicals R.sup.y, ##STR00004## R.sup.y are monovalent radicals or polyvalent radicals, which are optionally bonded to one another to form one or more 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.

2. The hydrosilylable mixture M of claim 1, wherein at least one compound A has the 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.

3. The hydrosilylable mixture M of claim 1, wherein compound B is selected from the group consisting of compounds of the formula IIIa
R.sup.4R.sup.5CCR.sup.6R.sup.7(IIIa),
of formula IIIb
R.sup.8CCR.sup.9(IIIb), and mixtures thereof, 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.

4. The hydrosilylable mixture M of claim 1, wherein R.sup.a is an unbranched alkyl radical or 2,6-dialkylated phenyl radical.

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

6. A method for hydrosilylating a mixture M comprising a compound A having at least one silicon-bonded hydrogen atom and a compound B having at least one carbon-carbon multiple bond, comprising: reacting compound A with compound B in the presence of a compound C as a hydrosilylation catalyst, wherein the compound C comprises at least one cationic Si(II) moiety, and the compound C comprises a cationic Si(II) compound of formula IV
([Si(II)Cp].sup.+).sub.aX.sup.a(IV) in which Cp is a -bonded cyclopentadienyl radical of formula V, which is substituted by radicals R.sup.y, ##STR00005## R.sup.y are monovalent radicals or polyvalent radicals, which are optionally bonded to one another to form one or more fused rings and X.sup. signifies an a valent anion, which does not react with cationic silicon(II) under the reaction conditions of hydrosilylation.

7. The method of claim 6, wherein the compound A has the 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.

8. The method of claim 6, wherein at least one compound B is selected from the group consisting of compounds of the formula IIIa
R.sup.4R.sup.5CCR.sup.6R.sup.7,(IIIa),
formula IIIb
R.sup.8CCR.sup.9(IIIb), and mixtures thereof, 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 claim 6, wherein R.sup.a is an unbranched alkyl radical or 2,6-dialkylated phenyl radical.

10. The method of claim 6, 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

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

(2) 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.

(3) 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.

(4) 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

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

(6) 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.

(7) 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

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

(9) 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.

(10) 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

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

(12) 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.

(13) 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.