CATIONIC GERMANIUM(II) COMPOUNDS, PROCESS FOR PREPARING SAME, AND THEIR USE AS CATALYSTS IN HYDROSILYLATION

Abstract

A mixture M includes at least one compound A, selected from (a1) a compound of the general formula (I) and/or (a2) a compound of the general formula (I′), at least one compound B, selected from (b1) a compound of the general formula (II) and/or (b2) a compound of the general formula (II′) and/or (b3) a compound of the general formula (II″), and at least one compound C, selected from cationic germanium(II) compounds of the general formula (III).

Claims

1-23. (canceled)

24. A mixture M comprising (a) at least one compound A selected from (a1) a compound of the general formula (I)
R.sup.1R.sup.2R.sup.3Si—H  (I), in which the radicals R.sup.1, R.sup.2 and R.sup.3 are each independently selected from the group consisting of (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbon radical, and (iv) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbonoxy radical, where two of the radicals R.sup.1, R.sup.2 and R.sup.3 may also form with each other a monocyclic or polycyclic, unsubstituted or substituted C.sub.2-C.sub.20-hydrocarbon radical, wherein substituted means in each case that the hydrocarbon or hydrocarbonoxy radical each independently has at least one of the following substitutions: a hydrogen atom can be replaced by halogen, —C≡N, —OR.sup.z, —SR.sup.z, —NR.sup.z.sub.2, —PR.sup.z.sub.2, —O—CO—R.sup.z, —NH—CO—R.sup.z, —O—CO—OR.sup.z or —COOR.sup.z, a CH.sub.2 group can be replaced by —O—, —S— or —NR.sup.z—, and a carbon atom can be replaced by a Si atom, in which R.sup.z is in each case independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl radical, C.sub.6-C.sub.14-aryl radical, and C.sub.2-C.sub.6-alkenyl radical; and/or (a2) a compound of the general formula (I′)
(SiO.sub.4/2).sub.a(R.sup.xSiO.sub.3/2).sub.b(HSiO.sub.3/2).sub.b′(R.sup.x.sub.2SiO.sub.2/2).sub.c(R.sup.xHSiO.sub.2/2).sub.c′(H.sub.2SiO.sub.2/2).sub.c″(R.sup.x.sub.3SiO.sub.1/2).sub.d(HR.sup.x.sub.2SiO.sub.1/2).sub.d′(H.sub.2R.sup.xSiO.sub.1/2).sub.d″(H.sub.3SiO.sub.1/2).sub.d′″  (I′), in which the radicals R.sup.x are each independently selected from the group consisting of (i) halogen, (ii) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbon radical, and (iii) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbonoxy radical, wherein substituted means in each case that the hydrocarbon or hydrocarbonoxy radical each independently has at least one of the following substitutions: a hydrogen atom can be replaced by halogen, a CH.sub.2 group can be replaced by —O— or —NR.sup.z—, in which R.sup.z is in each case independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl radical, C.sub.6-C.sub.14-aryl radical, and C.sub.2-C.sub.6-alkenyl radical; and in which the indices a, b, b′, c, c′, c″, d, d′, d″, d′″ specify the number of the respective siloxane unit in the compound and are each independently an integer in the range from 0 to 100 000, with the proviso that the sum of a, b, b′, c, c′, c″, d, d′, d″, d′″ together has the value of at least 2 and at least one of the indices b′, c′, c″, d′, d″ or d′″ is not equal to 0; and (b) at least one compound B selected from (b1) a compound of the general formula (II)
R.sup.4R.sup.5C═CR.sup.6R.sup.7  (II), and/or (b2) a compound of the general formula (II′)
R.sup.8C≡CR.sup.9  (II′) in which the radicals R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently selected from the group consisting of (i) hydrogen, (ii) —C≡N, (iii) organosilicon radical having 1-100 000 silicon atoms, (iv) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbon radical, and (v) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbonoxy radical, where two of the radicals R.sup.4, R.sup.5, R.sup.6 and R.sup.7 may also form with each other a monocyclic or polycyclic, unsubstituted or substituted C.sub.2-C.sub.20-hydrocarbon radical, wherein substituted means in each case that the hydrocarbon or hydrocarbonoxy radical each independently has at least one of the following substitutions: a hydrogen atom can be replaced by halogen, —C≡N, —OR.sup.z, —SR.sup.z, —NR.sup.z.sub.2, —PR.sup.z.sub.2, —O—CO—R.sup.z, —NH—CO—R.sup.z, —O—CO—OR.sup.z, —COOR.sup.z or —[O—(CH.sub.2).sub.n].sub.o—(CH(O)CH.sub.2) where n=1-6 and o=1-100, a CH.sub.2 group can be replaced by —O—, —S— or —NR.sup.z—, and a carbon atom can be replaced by a Si atom, in which R.sup.z is in each case independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.6-C.sub.14-aryl, and C.sub.2-C.sub.6-alkenyl; and/or b3) a compound (or a mixture of compounds) of the general formula (II″)
R.sup.x.sub.3Si—O[—SiR.sup.x.sub.2—O].sub.m—[Si(MB)R.sup.x—O].sub.n—SiR.sup.x.sub.3  (II″), in which the radicals R.sup.x are each independently selected from the group consisting of (i) hydrogen, (ii) halogen, (iii) MB, (iv) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbon radical, and (v) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbonoxy radical; and in which MB is each independently (i) —(CH.sub.2).sub.o—CR═CR.sub.2 or (ii) —(CH.sub.2).sub.o—C≡CR, where o=0-12 and R is in each case independently selected from the group consisting of (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbon radical, and (iv) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbonoxy radical, wherein substituted means in each case that the hydrocarbon or hydrocarbonoxy radical each independently has at least one of the following substitutions: a hydrogen atom can be replaced by halogen, —C≡N, —OR.sup.z, —SR.sup.z, —NR.sup.z.sub.2, —PR.sup.z.sub.2, —O—CO—R.sup.z, —NH—CO—R.sup.z, —O—CO—OR.sup.z or —COOR.sup.z, a CH.sub.2 group can be replaced by —O—, —S— or —NR.sup.z—, and a carbon atom can be replaced by a Si atom, in which R.sup.z is in each case independently selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl radical, C.sub.6-C.sub.14-aryl radical, and C.sub.2-C.sub.6-alkenyl radical; and in which m and n are each independently an integer in the range from 0 to 100 000, with the proviso that at least one radical MB is present in the compound; and (c) at least one compound C selected from the cationic germanium(II) compound of the general formula (III)
([Ge(II)Cp].sup.+).sub.aX.sup.a−  (III), in which Cp is a π-bonded cyclopentadienyl radical of the general formula (IIIa) ##STR00003## in which the radicals R.sup.y are each independently selected from the group consisting of (i) triorganosilyl radical of the formula —SiR.sup.b.sub.3, in which the radicals R.sup.b are each independently C.sub.1-C.sub.20-hydrocarbon radical, (ii) hydrogen, (iii) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbon radical, and (iv) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbonoxy radical, wherein in each case two radicals R.sup.y can also form with each other a monocyclic or polycyclic C.sub.2-C.sub.20-hydrocarbon radical, and wherein substituted means in each case that in the hydrocarbon or hydrocarbonoxy radical also at least one carbon atom can be replaced by a Si atom. X.sup.a− is an a valent anion; and a can have the values 1, 2 or 3.

25. The mixture M as claimed in claim 24, wherein in formula (I) the radicals R.sup.1, R.sup.2 and R.sup.3 are each independently selected from the group consisting of (i) hydrogen, (ii) chlorine, (iii) unsubstituted or substituted C.sub.1-C.sub.12-hydrocarbon radical, and (iv) unsubstituted or substituted C.sub.1-C.sub.12-hydrocarbonoxy radical, wherein substituted has the same definition as before; and in formula (I′) the radicals R.sup.x are each independently selected from the group consisting of chlorine, C.sub.1-C.sub.6-alkyl radical, C.sub.2-C.sub.6-alkenyl radical, phenyl, and C.sub.1-C.sub.6-alkoxy radical, and the indices a, b, b′, c, c′, c″, d, d′, d″, d′″ are each independently selected from an integer in the range of 0 to 1.

26. The mixture M as claimed in claim 25, wherein in formula (I) the radicals R.sup.1, R.sup.2 and R.sup.3 are each independently selected from the group consisting of (i) hydrogen, (ii) chlorine, (iii) C.sub.1-C.sub.6-alkyl radical, (iv) C.sub.2-C.sub.6-alkenyl radical, (v) phenyl, and (vi) C.sub.1-C.sub.6-alkoxy radical; and in formula (I′) the radicals R.sup.x are each independently selected from the group consisting of chlorine, methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, and phenyl, and the indices a, b, b′, c, c′, c″, d, d′, d″, d′″ are each independently selected from an integer in the range from 0 to 1000.

27. The mixture M as claimed in claim 26, wherein in formula (I) the radicals R.sup.1, R.sup.2 and R.sup.3 and in formula (I′) the radicals R.sup.x are each independently selected from the group consisting of hydrogen, chlorine, methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, and phenyl, and the indices a, b, b′, c, c′, c″, d, d′, d″, d′″ are each independently selected from an integer in the range from 0 to 1000.

28. The mixture M as claimed in claim 24, wherein in the formulae (II) and (II′) the radicals R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently selected from the group consisting of (i) hydrogen, (ii) —C≡N, (iii) unsubstituted or substituted C.sub.1-C.sub.12-hydrocarbon radical, (iv) unsubstituted or substituted C.sub.1-C.sub.12-hydrocarbonoxy radical, wherein two of the radicals R.sup.4, R.sup.5, R.sup.6 and R.sup.7 may also form with each other a monocyclic or polycyclic, unsubstituted or substituted C.sub.2-C.sub.20-hydrocarbon radical, wherein substituted means in each case that the hydrocarbon or hydrocarbonoxy radical each independently has at least one of the following substitutions: a hydrogen atom can be replaced by halogen, —C≡N, C.sub.1-C.sub.6-alkoxy, —NR.sup.z.sub.2, —O—CO—R.sup.z, —NH—CO—R.sup.z, —O—CO—OR.sup.z, —COOR.sup.z or —[O—(CH.sub.2).sub.n].sub.o—(CH(O)CH.sub.2) where n=1-3 and o=1-20, in which R.sup.z is in each case independently selected from the group consisting of hydrogen, chlorine, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, and phenyl; and (v) organosilicon radical selected from the general formula (IIa),
—(CH.sub.2).sub.n—SiR.sup.x.sub.3  (IIa), in which the radicals R.sup.x are each independently selected from the group consisting of (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbon radical, and (iv) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbonoxy radical, wherein substituted means in each case that the hydrocarbon or hydrocarbonoxy radical each independently has at least one of the following substitutions: a hydrogen atom can be replaced by halogen, a CH.sub.2 group can be replaced by —O— or —NR.sup.z—, in which R.sup.z is selected from the group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.6-C.sub.14-aryl, and C.sub.2-C.sub.6-alkenyl; and in which n=0-12; and where in formula (II″) the radicals R.sup.x are each independently selected from the group consisting of (i) hydrogen, (ii) chlorine, (iii) C.sub.1-C.sub.6-alkyl radical, (iv) phenyl, (v) MB and (vi) C.sub.1-C.sub.6-alkoxy radical, where MB is in each case independently (i) —(CH.sub.2).sub.o—CR═CR.sub.2 or (ii) —(CH.sub.2).sub.o—C≡CR, where o=0-6 and in which R is in each case independently selected from the group consisting of (i) hydrogen, (ii) chlorine, (iii) C.sub.1-C.sub.6-alkyl radical, (iv) phenyl, and (v) C.sub.1-C.sub.6-alkoxy radical.

29. The mixture M as claimed in claim 28, wherein in the formula (II) and (II′) the radicals R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are each independently selected from the group consisting of (i) hydrogen, (ii) —C≡N, (iii) organosilicon radical having 1-100 000 silicon atoms selected from the general formula (IIa), in which the radicals R.sup.x are each independently selected from the group consisting of hydrogen, chlorine, C.sub.1-C.sub.6-alkyl radical, C.sub.2-C.sub.6-alkenyl radical, phenyl and C.sub.1-C.sub.6-alkoxy radical; (iv) unsubstituted or substituted C.sub.1-C.sub.6-hydrocarbon, and (v) unsubstituted or substituted C.sub.1-C.sub.6-hydrocarbonoxy radical, wherein substituted means in each case that the hydrocarbon or hydrocarbonoxy radical has each independently at least one of the following substitutions: a hydrogen atom can be replaced by chlorine, —C≡N, —O—CH.sub.2—(CH(O)CH.sub.2) (=glycidoxy radical), —NR.sup.z.sub.2 and —O—CO—R.sup.z, wherein R.sup.z is in each case independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6-alkyl; and where in formula (II″) the radicals R.sup.x are each independently selected from the group consisting of C.sub.1-C.sub.3-alkyl radical and MB, where MB is in each case —(CH.sub.2)O—CR═CR.sub.2, in which R is in each case hydrogen and o=0-6.

30. The mixture M as claimed in claim 24, wherein in formula (III) the radicals R.sup.y are each independently selected from the group consisting of (i) C.sub.1-C.sub.3-alkyl radical and (ii) triorganosilyl radical of the formula —SiR.sup.b.sub.3, in which the radicals R.sup.b are each independently C.sub.1-C.sub.20-alkyl radicals.

31. The mixture M as claimed in claim 30, wherein in formula (III) the anions X— are selected from the group consisting of the compounds of the formulae [B(R.sup.a).sub.4].sup.− and [Al(R.sup.a).sub.4].sup.−, in which the radicals R.sup.a are in each case independently selected from aromatic C.sub.6-C.sub.14-hydrocarbon radicals in which at least one hydrogen atom has been mutually independently substituted by a radical selected from the group consisting of (i) fluorine, (ii) perfluorinated C.sub.1-C.sub.6-alkyl radical, and (iii) triorganosilyl radical of the formula —SiR.sup.b.sub.3, in which the radicals R.sup.b are each independently C.sub.1-C.sub.20-alkyl radicals.

32. The mixture M as claimed in claim 31, wherein in formula (III) all radicals R.sup.y are methyl and the anions X— are selected from the group consisting of the compounds of the formulae [B(R.sup.a).sub.4].sup.−, in which the radicals R.sup.a are each independently selected from aromatic C.sub.6-C.sub.14-hydrocarbon radicals, in which all hydrogen atoms have been mutually independently substituted by a radical selected from the group consisting of (i) fluorine and (ii) triorganosilyl radicals of the formula —SiR.sup.b.sub.3, in which the radicals R.sup.b are each independently C.sub.1-C.sub.20-alkyl radicals.

33. The mixture M as claimed in claim 32, wherein the compound C is selected from the group consisting of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.−; Cp*Ge.sup.+ B[C.sub.6F.sub.4(4-TBS)].sub.4.sup.−, where TBS=SiMe.sub.2tert-butyl; Cp*Ge.sup.+ B(2-NaphF).sub.4.sup.−, where 2-NaphF=perfluorinated 2-naphthyl radical; and Cp*Ge.sup.+ B[(C.sub.6F.sub.5).sub.3(2-NaphF)].sup.−, where 2-NaphF=perfluorinated 2-naphthyl radical.

34. A process for hydrosilylation of the mixture M as claimed in claim 24, wherein at least one compound A is reacted with at least one compound B in the presence of at least one compound C and in the presence of oxygen.

35. The process as claimed in claim 34, wherein the temperature is in a range from −100° C. to +250° C. and the pressure is in a range from 0.01 bar to 100 bar.

36. The process as claimed in claim 34, wherein the oxygen originates from an oxygen-containing gas mixture having an oxygen content of 0.1-100% by volume.

37. The process as claimed in claim 36, wherein the reaction is carried out under an air, lean air or oxygen atmosphere.

38. The process as claimed in claim 34, wherein the molar ratio between the compound C and the Si—H groups present in the compound A is in a range from 1:10.sup.7 to 1:1.

39. A cationic germanium(II) compound of the general formula (IV)
[Cp*Ge].sup.+[B(R.sup.a).sub.4].sup.−  (IV), in which Cp* is a π-bonded pentamethylcyclopentadienyl radical, and the radicals R.sup.a are each independently selected from aromatic C.sub.6-C.sub.14-hydrocarbon radicals, in which at least one hydrogen atom has been mutually independently substituted by a radical selected from the group consisting of (i) fluorine, (ii) perfluorinated C.sub.1-C.sub.6-alkyl radical, and (iii) triorganosilyl radical of the formula —SiR.sup.b.sub.3, in which the radicals R.sup.b are each independently C.sub.1-C.sub.20-alkyl radicals.

40. The cationic germanium(II) compound as claimed in claim 39, wherein the radicals R.sup.a are each independently selected from aromatic C.sub.6-C.sub.14-hydrocarbon radicals, in which all hydrogen atoms have been mutually independently substituted by a radical selected from the group consisting of (i) fluorine and (ii) triorganosilyl radical of the formula —SiR.sup.b.sub.3, in which the radicals R.sup.b are each independently C.sub.1-C.sub.20-alkyl radicals.

41. The cationic germanium (II) compound as claimed in claim 40, wherein the compound is selected from the group consisting of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.−; Cp*Ge.sup.+ B[C.sub.6F.sub.4(4-TBS)].sub.4.sup.−, where TBS=SiMe.sub.2tert-butyl; Cp*Ge.sup.+ B(2-NaphF).sub.4.sup.−, where 2-NaphF=perfluorinated 2-naphthyl radical; and Cp*Ge.sup.+ B[(C.sub.6F.sub.5).sub.3(2-NaphF)].sup.−, where 2-NaphF=perfluorinated 2-naphthyl radical.

42. A method for preparing cationic germanium(II) compounds of the general formula (III)
([Ge(II)Cp].sup.+).sub.aX.sup.a−  (III)
wherein
(a)[Cp.sub.2Ge(II)]  (V), in which the radicals Cp are each independently a π-bonded cyclopentadienyl radical of the general formula (Va) ##STR00004## in which the radicals R.sup.y are each independently selected from the group consisting of (i) triorganosilyl radical of the formula —SiR.sup.b.sub.3, in which the radicals R.sup.b are each independently C.sub.1-C.sub.20-alkyl radicals, (ii) hydrogen, (iii) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbon radical, and (iv) unsubstituted or substituted C.sub.1-C.sub.20-hydrocarbonoxy radical, wherein in each case two radicals R.sup.y can also form with each other a monocyclic or polycyclic C.sub.2-C.sub.20-hydrocarbon radical, and wherein substituted means in each case that in the hydrocarbon or hydrocarbonoxy radical also at least one carbon atom can be replaced by a Si atom, with the proviso that in at least one Cp radical at least one radical R.sup.y is a —CHR.sup.1R.sup.2 group, in which R.sup.1 and R.sup.2 are each independently selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.19-alkyl radical and (iii) C.sub.6-C.sub.19-aryl radical; is reacted with (b) a carbocationic compound of the general formula (VI)
(R.sup.d.sub.3C.sup.+).sub.aX.sup.a−  (VI), in which a can take the values 1, 2 or 3; and in which X.sup.a− is an a valent anion; and in which the radicals R.sup.d are each independently selected from unsubstituted or substituted, aromatic C.sub.6-C.sub.14-hydrocarbon radicals, wherein substituted means that the hydrocarbon radical each independently has at least one of the following substitutions: a hydrogen atom can be replaced by halogen or C.sub.1-C.sub.6-alkyl radical.

43. A catalyst system comprising at least one cationic germanium(II) compound of the general formula (IV) according to claim 39 and oxygen.

44. The use of cationic germanium(II) compounds of the general formula (III) according to claim 24 as a catalyst.

45. The use as claimed in claim 44, wherein the cationic germanium(II) compound is one of the general formula (IV) according to claim 39.

Description

EXAMPLES

[0081] The following tritylium salts were prepared analogously to the following literature references:

(C.sub.6H.sub.5).sub.3C.sup.+ B[C.sub.6F.sub.4(4-TBS)].sub.4.sup.−, TBS=SiMe.sub.2tert-butyl: Marks et al., Organometallics 1997, 16, 842-857).
Decamethylgermanocene: Weidenbruch et al., J. Organomet. Chem. 2006, 691, 809-810. (C.sub.6H.sub.5).sub.3C.sup.+ B(Naph.sup.F).sub.4.sup.− and (C.sub.6H.sub.5).sub.3C.sup.+ B[(C.sub.6F.sub.4).sub.3(Naph)].sup.− where Naph.sup.F=perfluoro-ß-naphthyl: Mathur und Strickler, US 2015/0259362 (2017); Berris, WO2007/070770 (2007).

Comparative Example 1 with Exclusion of Oxygen—Non-Inventive

[0082] All steps were carried out under argon. 2.0 mg (2.3 μmol) of Cp*Ge B(C.sub.6F.sub.5).sub.4.sup.− were dissolved in 801 mg of CD.sub.2Cl.sub.2 and added to a mixture of 238 mg (2.01 mmol) of α-methylstyrene and 303 mg (2.03 mmol) of 1,1,3,3,3-pentamethyldisiloxane and the mixture shaken. The solution was analyzed by .sup.1H-NMR spectroscopy after 9 days. No hydrosilylation was detectable.

Example 1: Preparation of Cp*Ge.SUP.+ B(C.SUB.6.F.SUB.5.).SUB.4..SUP.−

[0083] Under an argon atmosphere, 701 mg (2.04 mmol) of decamethylgermanocene (Cp*.sub.2Ge, Cp*=pentamethylcyclopentadienyl) were dissolved in 5 ml of dichloromethane and a solution of 1.70 g (1.83 mmol) of (C.sub.6H.sub.5).sub.3C.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− in 5 ml of dichloromethane was added slowly at room temperature with shaking. Subsequently, enough heptane was added as precipitant until no further precipitation of the product took place. The supernatant solution was decanted off, the precipitate was redissolved in dichloromethane and again precipitated with heptane. The precipitated product was filtered off under suction and dried, finally under high vacuum.

[0084] Yield: 1.63 g (97%), pale pink solid.

[0085] .sup.1H-NMR (CD.sub.2Cl.sub.2): 6=2.23 (methyl groups).

[0086] .sup.13C-NMR (CD.sub.2Cl.sub.2): 6=8.82 (methyl groups), 6=123.1 (C's Cp*-Ring), 6=124 (broad), 6=135.3 (m), 6=137.3 (m), 6=139.2 (m), 6=147.2 (m), 6=149.1 (m): aromatic C—F.

[0087] .sup.11B-NMR (CD.sub.2Cl.sub.2): δ=−16.66 (s).

[0088] .sup.19F-NMR (CD.sub.2Cl.sub.2): δ=−167.4 (mc, 8 ortho-F), δ=−163.5 (mc, 4 para-F), δ=−132.9 (m, broad, 8 meta-F).

[0089] The crystalline solid was stored in air for 4 days and showed no visible change; the NMR spectrum was identical to that of the freshly prepared pure substance.

Example 2: Preparation of Cp*Ge.SUP.+ B[C.SUB.6.F.SUB.4.(4-TBS)].SUB.4..SUP.−

[0090] 365.1 mg (0.279 mmol) of (C.sub.6H.sub.5).sub.3C.sup.+ B[C.sub.6F.sub.4(4-TBS)].sub.4.sup.− were dissolved in 965 mg of CD.sub.2Cl.sub.2 and the solution cooled to −30° C. 114.8 mg (0.335 mmol) of decamethylgermanocene (air-sensitive!) dissolved in ca. 350 mg of CD.sub.2Cl.sub.2 were slowly added under argon. The initially dark orange solution lightened to a pale yellowish color. 4 ml of pentane were added, the product precipitated as a beige solid and was washed with small portions of pentane. The solid was dried in vacuo. Yield: 300 mg (85%), beige solid.

[0091] .sup.1H-NMR (CD.sub.2Cl.sub.2): δ=0.352 (s, 2 Si—CH.sub.3), δ=0.913 s (Si-tert butyl), δ=2.17 (s, 15H, Cp*).

[0092] .sup.29Si-NMR (CD.sub.2Cl.sub.2): δ=5.63 (s, aromatic silyl group)

[0093] .sup.19F-NMR (CD.sub.2Cl.sub.2): δ=−132.2 (m, 8F), δ=−130.4 (m, 8F).

Example 3: Preparation of Cp*Ge.SUP.+ B(Naph.SUP.F.).SUB.4..SUP.− where Naph^{F.=Heptafluoro-ß-Naphthyl}

[0094] The preparation was carried out as in example 2 by reacting decamethylgermanocene with (C.sub.6H.sub.5).sub.3C.sup.+ B(Naph.sup.F).sub.4.sup.−.

[0095] Yield: 92%, beige solid.

[0096] .sup.1H-NMR (CD.sub.2Cl.sub.2): δ=2.22 (s, 15H, Cp*).

[0097] .sup.19F-NMR (CD.sub.2Cl.sub.2): δ=−161.3 to −160.9 (m, 4F), −159.8 to −159.4 (4F), −155.8 to −154.7 (4F), −150.2 to −149.8 (4F), −146.4 to −145.7 (4F), −125.9 to −124.4 (4F), −109.8 (mc, 1F), −109.3 (mc, 1F), −108.6 to −107.7 (m, 1F), −106.5 (mc, 1F).

[0098] .sup.11B-NMR (CD.sub.2Cl.sub.2): δ=−13.80.

Example 4: Preparation of Cp*Ge.SUP.+ B[(C.SUB.6.F.SUB.4.).SUB.3.(Naph)].SUP.− where Naph^{F.=Perfluoro-ß-Naphthyl}

[0099] The preparation was carried out as in example 2 by reacting decamethylgermanocene with (C.sub.6H.sub.5).sub.3C.sup.+ B[(C.sub.6F.sub.4).sub.3(Naph.sup.F)].sup.−.

[0100] Yield: 70%, beige solid.

[0101] .sup.1H-NMR (CD.sub.2Cl.sub.2): δ=2.22 (s, 15H, Cp*).

[0102] .sup.11B-NMR (CD.sub.2Cl.sub.2): δ=−16.45.

Example 5: Hydrosilylation of α-Methylstyrene with Dimethylphenylsilane

[0103] 207 mg (1.75 mmol) of α-methylstyrene and 229 mg (1.68 mmol) of dimethylphenylsilane together with 650 mg of CD.sub.2Cl.sub.2 were weighed into a reaction vessel under argon and 1.7 mg (1.92 μmol, 0.11 mol % based on dimethylphenylsilane) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− in 160 mg CD.sub.2Cl.sub.2 were added. A syringe was used to inject 3 ml of air into the mixture. The reaction was complete after 24 hours at room temperature. This gave phenyl-CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2Ph.

[0104] Product purity (GC)>90%,

[0105] .sup.1H-NMR (CD.sub.2Cl.sub.2): δ=0.43 and 0.49 (s, 2 CH.sub.3), δ=1.52 (mc, CH.sub.2), δ=1.56 (d, CH3), δ=3.20 (mc, CH), δ=7.40-7.50 (m, 3 aromatic H), δ=7.50-7.58 (m, 2 aromatic H), δ=7.59-7.66 (m, 3 aromatic H), δ=7.76-7.82 (m, 2 aromatic H).

Example 6: Hydrosilylation of α-Methylstyrene with Dimethylphenylsilane

[0106] 120 mg (1.01 mmol) of α-methylstyrene and 137 mg (1.01 mmol) of dimethylphenylsilane together with 400 mg of CD.sub.2Cl.sub.2 were weighed into a reaction vessel under argon and 1.2 mg (0.94 μmol, 0.09 mol % based on dimethylphenylsilane) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− in 130 mg CD.sub.2Cl.sub.2 were added. A syringe was used to inject 3 ml of air into the mixture. The reaction was complete after 24 hours at room temperature. This gave phenyl-CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2Ph.

[0107] Product purity (GC)>90%,

[0108] .sup.1H-NMR (CD.sub.2Cl.sub.2): δ=0.43 and 0.49 (s, 2 CH.sub.3), δ=1.52 (mc, CH.sub.2), δ=1.56 (d, CH3), δ=3.20 (mc, CH), δ=7.40-7.50 (m, 3 aromatic H), δ=7.50-7.58 (m, 2 aromatic H), δ=7.59-7.66 (m, 3 aromatic H), δ=7.76-7.82 (m, 2 aromatic H).

Example 7: Hydrosilylation of α-Methylstyrene with Pentamethyldisiloxane

[0109] 1.7 mg (1.9 μmol) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− were dissolved in 890 mg of CD.sub.2Cl.sub.2 and a total of ca. 0.6 ml (ca. 30 μmol) of oxygen was introduced at room temperature over a period of 15 minutes with exclusion of air. The solution was added to a mixture of 208 mg (1.76 mmol) of α-methylstyrene and 260 mg (1.75 mmol) of 1,1,3,3,3-pentamethyldisiloxane and the mixture was shaken. After 3 hours the conversion was ca. 35% and after 24 hours conversion was complete. The hydrosilylation product formed was phenyl-CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2—O—Si (CH.sub.3).sub.3, which was verified by means of .sup.1H-NMR investigation in CD.sub.2Cl.sub.2 and comparison with an authentic sample.

Example 8: Hydrosilylation of α-Methylstyrene with Pentamethyldisiloxane

[0110] 1.7 mg (1.9 μmol) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− were dissolved in 890 mg of CD.sub.2Cl.sub.2 and a total of ca. 8 ml (ca. 0.4 mmol) of oxygen was introduced at room temperature over a period of 3 hours with exclusion of air. The hydrosilylation was carried out as in Example 5. After 4 hours the conversion was ca. 83% and after 6 hours conversion was complete. The hydrosilylation product formed was phenyl-CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2—O—Si (CH.sub.3).sub.3, which was verified by means of .sup.1H-NMR investigation in CD.sub.2Cl.sub.2 and comparison with an authentic sample.

Example 9: Hydrosilylation of α-Methylstyrene with Pentamethyldisiloxane

[0111] 1.6 mg (1.8 μmol) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− were dissolved in 900 mg of CD.sub.2Cl.sub.2 and a total of ca. 1.2 ml (ca. 60 μmol) of oxygen were introduced at room temperature over a period of 30 minutes with exclusion of air. After a standing time of 23 hours, the hydrosilylation was carried out with this solution as in example 5. After 3 hours the conversion was ca. 65% and after 15 hours conversion was complete. The hydrosilylation product formed was phenyl-CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2—O—Si (CH.sub.3).sub.3, which was verified by means of .sup.1H-NMR investigation in CD.sub.2Cl.sub.2 and comparison with an authentic sample.

Example 10: Hydrosilylation of α-Methylstyrene with Pentamethyldisiloxane

[0112] 299 mg (2.01 mmol) of pentamethyldisiloxane and 248 mg (2.10 mmol) of α-methylstyrene are mixed and a solution of 2.5 mg (2.03 μmol, 0.1 mol %) of Cp*Ge.sup.+ B(Naph.sup.F).sub.4.sup.− in 361 mg of CD.sub.2Cl.sub.2 was added under argon. 1 ml of air is added 3 times in succession to the gas space above the solution and the mixture shaken for ca. 30 seconds each time. The hydrosilylation is monitored by .sup.1H-NMR spectroscopy at room temperature. The conversion is 35% after 6 hours.

Example 11: Hydrosilylation of 1-hexene with 1,1,3,3,3-pentamethyldisiloxane

[0113] 139 mg (1.66 mmol) of 1-hexene, 203 mg (1.37 mmol) of 1,1,3,3,3-pentamethyldisiloxane and 500 mg CD.sub.2Cl.sub.2 and a solution of 2.8 mg (3.16 μmol, 0.23 mol % based on 1,1,3,3,3-pentamethyldisiloxane) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− in 170 mg CD.sub.2Cl.sub.2 were mixed in a reaction vessel under argon. 3 ml of air (ca. 0.8 mg of O.sub.2, corresponds to ca. 25 μmol) were added to the gas space using a syringe, the vessel sealed and heated at 45° C. for 4 hours. The gas chromatographic analysis showed a conversion of 90%. The main product of the reaction is CH.sub.3—(CH.sub.2).sub.5—Si(CH.sub.3).sub.2—O—Si(CH.sub.3).sub.3. The identification was carried out by comparison with an authentic substance sample.

Example 12: Hydrosilylation of α-methylstyrene with 1,1,3,3,3-pentamethyldisiloxane

[0114] The working steps were carried out in air at room temperature.

[0115] 815 mg (6.90 mmol) of α-methylstyrene and 1116 mg (7.52 mmol) of 1,1,3,3,3-pentamethyldisiloxane were mixed and 1.1 mg (0.865 mmol, 0.0125 mol % based on α-methylstyrene) of Cp*Ge.sup.+ B[C.sub.6F.sub.4(4-TBS)].sub.4.sup.− were added. Conversion was complete after 24 hours. The hydrosilylation product formed was phenyl-CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2—O—Si (CH.sub.3).sub.3, which was verified by means of .sup.1H-NMR investigation in CD.sub.2Cl.sub.2 and comparison with an authentic sample.

Example 13: Hydrosilylation of α-methylstyrene with 1,1,3,3,3-pentamethyldisiloxane

[0116] The working steps were carried out in air at room temperature.

[0117] 805 mg (6.81 mmol) of α-methylstyrene and 1009 mg (6.80 mmol) of 1,1,3,3,3-pentamethyldisiloxane were mixed and a solution of 9.2 mg (7.23 μmol, 0.106 mol % based on 1,1,3,3,3-pentamethyldisiloxane) of Cp*Ge.sup.+ B[C.sub.6F.sub.4(4-TBS)].sub.4.sup.− dissolved in 941 mg of CD.sub.2Cl.sub.2 was added with stirring. The mixture was diluted with a further 924 mg of CD.sub.2Cl.sub.2. After 3 hours the conversion was 91% and after 24 hours conversion was complete. The hydrosilylation product formed was phenyl-CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2—O—Si(CH.sub.3).sub.3, which was verified by means of .sup.1H-NMR investigation in CD.sub.2Cl.sub.2 and comparison with an authentic sample.

[0118] After further addition of a mixture of 301 mg (2.55 mmol) of α-methylstyrene and 376 mg (2.53 mmol) of 1,1,3,3,3-pentamethyldisiloxane, the conversion was again complete after 24 hours, i.e. the product solution still contained active germanium(II) species.

[0119] After further addition of a mixture of 806 mg (6.82 mmol) of α-methylstyrene and 1003 mg (6.76 mmol) of 1,1,3,3,3-pentamethyldisiloxane, the conversion was again complete after 24 hours, i.e. the product solution still contained active germanium(II) species.

Example 14: Hydrosilylation of α-methylstyrene with 1,1,3,3,3-pentamethyldisiloxane

[0120] The working steps were carried out in air at room temperature.

[0121] 801 mg (6.78 mmol) of α-methylstyrene and 1005 mg (6.78 mmol) of 1,1,3,3,3-pentamethyldisiloxane were mixed, 900 mg of CD.sub.2Cl.sub.2 were added and a solution of 0.9 mg (0.708 μmol, 0.010 mol % based on 1,1,3,3,3-pentamethyldisiloxane) of Cp*Ge.sup.+ B[C.sub.6F.sub.4(4-TBS)].sub.4.sup.− dissolved in 922 mg of CD.sub.2Cl.sub.2 was added with stirring. The reaction was complete after 24 hours. The hydrosilylation product formed was phenyl —CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2—O— Si(CH.sub.3).sub.3, which was verified by means of .sup.1H-NMR investigation in CD.sub.2Cl.sub.2 and comparison with an authentic sample.

Example 15: Hydrosilylation of α-methylstyrene with 1,1,3,3,3-pentamethyldisiloxane

[0122] In a glove box, under an argon atmosphere, 300 mg (2.02 mmol) of 1,1,3,3,3-pentamethyldisiloxane and 242 mg (2.05 mmol) of α-methylstyrene were mixed in an NMR tube and a solution of 1.9 mg (2.1 μmol) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− in 807 mg of d.sup.8-toluene was added. After 9 days storage under argon, no reaction had taken place. The tube was opened and 1 ml of air (ca. 9 μmol of oxygen) was added. After 24 hours the conversion was 53% and after a further 3 days hydrosilylation was complete. The hydrosilylation product formed was phenyl —CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2—O—Si(CH.sub.3).sub.3, which was verified by means of .sup.1H-NMR investigation in d.sup.8-toluene and comparison with an authentic sample.

Example 16: Hydrosilylation of α-methylstyrene with 1,1,3,3,3-pentamethyldisiloxane

[0123] The experiment according to Example 15 was repeated using CD.sub.2Cl.sub.2 instead of d.sup.8-toluene. After 9 days storage under argon, no reaction had taken place. The tube was opened and 1 ml of air (ca. 9 μmol of oxygen) was added. After 24 hours the conversion was 33% and after 2 days conversion was complete. The hydrosilylation product formed was phenyl-CH(CH.sub.3)—CH.sub.2—Si(CH.sub.3).sub.2—O—Si(CH.sub.3).sub.3, which was verified by means of .sup.1H-NMR investigation in CD.sub.2Cl.sub.2 and comparison with an authentic sample.

Example 17: Hydrosilylation of Phenylacetylene with Triethylsilane

[0124] 150 mg (1.47 mmol) of phenylacetylene, 171 mg (1.47 mmol) of triethylsilane and 616 mg of CD.sub.2Cl.sub.2 were mixed in a reaction vessel under argon and a solution of 1.4 mg (1.58 μmol, 0.11 mol % based on reactants) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− in 100 mg CD.sub.2Cl.sub.2 were added. 3 ml of air (ca. 0.8 mg of 02, corresponds to ca. 25 μmol) were added to the gas space using a syringe, the vessel sealed and heated at 50° C. for 40 hours. The following hydrosilylation products were detected in the specified proportions by gas chromatographic and GC/MS analysis: 60% Ph-CH═CH-SiEt.sub.3, 10% Ph-CH.sub.2—CH(SiEt.sub.3).sub.2.

Example 18: Hydrosilylation of 1-Hexyne with Triethylsilane

[0125] The reaction was carried out as in Example 17 at 50° C. with 103 mg (1.26 mmol) of 1-hexyne, 142 mg (1.22 mmol) of triethylsilane, 1.2 g of dichloromethane and 1.3 mg (1.41 μmol) of Cp*Ge.sup.+ B(C.sub.6F.sub.5).sub.4.sup.− in 100 mg of CD.sub.2Cl.sub.2. The reaction time was 19 hours. Ca. 30% C.sub.4H.sub.9—CH═CH-SiEt.sub.3 were detected by gas chromatographic and GC/MS analysis.