- Stereoselective synthesis of (E)- and (Z)-triethoxy(vinyl-d 2)silanes by hydrosilylation of acetylene-d 2
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The hydrosilylation of deuterated acetylene with triethoxysilane can be directed to the synthesis of either cis or trans triethoxy(vinyl-d 2)silanes by an appropriate choice of metal catalyst. In addition, we have demonstrated the viability of designing hydrosilylation-arylation sequential processes in which acetylene can be converted into styrenes or stilbenes using the same Pd catalyst for both reactions.
- Gordillo, Alvaro,Forigua, Johan,Lopez-Mardomingo, Carmen,De Jesus, Ernesto
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experimental part
p. 352 - 355
(2011/03/21)
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- Competitive dehydrogenative silylation and hydrogenative dimerization of vinyltriethoxysilane catalyzed by the [Ni(acac)2] + PPh3 system, intermediate and mechanistic implications
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[Ni(acac)C2H5(PPh3)] (C) has been shown to be an essential intermediate in the reaction between HSi(OC2H5)3 and vinyltrisubstituted silanes catalyzed by the system [Ni(acac)2] + PPh3 at room temperature, but only after oxygenation of the coordinated triphenylphosphine. The stoichiometric and catalytic reactions of complex C with the substrates lead to catalysed, competitive dehydrogenative silylation and hydrogenative dimerization of vinylsilane, which occur following insertion of the latter into Ni-H, Ni-Si ≡ and Ni-C bonds.
- Marciniec,Maciejewski,Gulinski,Maciejewska,Duczmal
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p. 245 - 251
(2007/10/03)
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- Catalysis of hydrosilylation. Part XXV. Effect of nickel(0) and nickel(II) complex catalysts on dehydrogenative silylation, hydrosilylation and dimerization of vinyltriethoxysilane
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General catalysis by Ni(O) and Ni(II) phosphine and non-phosphine complexes of the competitive-consecutive reaction of vinyltriethoxysilane with triethoxysilane has been observed to give mainly products of dehydrogenative silylation and hydrogenative dimerization accompanied by products of regular hydrosilylation, disproportionation of substrates and secondary reactions of the product-bis(silyl)ethene.In an excess of vinylsilane, side reactions can be practically eliminated.Tertiary phosphine and phosphite ligands of nickel acetylacetonate (Ni(acac)2*2PR3) stop the consecutive reactions of bis(silyl)ethene but in the presence of ?-basic and bulky tricyclohexylphosphine the system catalyzes selectively the regular hydrosilylation of bis(silyl)ethene.Keywords: Nickel; Silicon; Hydrosilylation; Silane; Catalysis
- Marciniec, Bogdan,Maciejewski, Hieronim,Rosenthal, Uwe
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p. 147 - 152
(2007/10/02)
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- Catalysis of hydrosilylation XXIII. Effect of substituents at silicon on unusual hydrosilylation of vinylsilanes catalysed by nickel acetylacetonate
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Nickel acetylacetonate catalyses a competitive-consecutive reaction of trisubstituted silanes ((EtO)3SiH and Et3SiH) with a variety of vinyl-trisubstituted silanes, giving products of dehydrogenative silylation, hydrosilylation and hydrogenative oligimerization as well as of disproportionation of substrates and dehydrogenative silylation of bis(silyl)ethenes.The conversion, yield and selectivities of the reaction have been influenced by many factors such as electronic and steric effects of the substituents at silicon of both initial substrates, as well as by the vinyl:hydrosilane ratio, the temperature and the presence of dioxygen.
- Marciniec, Bogdan,Maciejewski, Hieronim
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- CATALYSIS OF HYDROSILYLATION. PART II. ADDITION OF TRIALKOXYSILANES TO VINYLTRIALKOXYSILANES CATALYZED BY TRANSITION METAL COMPLEXES
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Hydrosilylation of vinyltrialkoxysilanes by trialkoxysilanes catalyzed by various transition metal complexes: H2PtCl6, (PPh3)3RhCl, (PPh3)3RuCl2, Ru(acac)3, Ni(acac)2 was found to proceed giving mostly 1,2-bis(trialkoxysilyl)ethane (β-adduct) as the main product.In presence of ruthenium complexes, besides β-adduct, unsaturated product of dehydrogenative double hydrosilylation (RO)3SiCH=CHSi(OR)3 (where R=C2H5, iso-C3H7) was obtained as a by-product, except for trimethoxysilyl derivatives, where α-adduct was found.Addition of trialkoxysilane to vinyltrialkoxysilanecontaining different substituents at two silicon atoms proceeds via RO/R'O exchange of the successive substituents, followed by hydrosilylation of all vinylsilanes by all trisubstituted silanes.
- Marciniec, Bogdan,Gulinski, Jacek,Urbaniak, Wlodzimierz
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p. 287 - 296
(2007/10/02)
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