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The reaction of hydrosilylation of allyl esters XOCH2CH=CH2 (X = MeCO, CF3CO, C3F7CO) and PhOCH2CH=CH2 with hydrosilanes HSiY3 (Y = Cl, OEt) in the presence of the Speier catalyst, the Speier catalyst with additives, and of various nickel complexes was studied. The catalytic hydrosilylation reaction in the presence of the Speier catalyst is accompanied by the reduction. Additives to the Speier catalyst (vinyltriethoxysilane and some ethers) allow to suppress considerably the reduction reaction. In the presence of the studied nickel complexes mainly reduction and isomerization reactions occurred. The best nickel catalysts of hydrosilylation were the mixtures of NiCl2 or Ni(acac)2 with phosphine oxides. In contrast to allyl esters, the hydrosilylation of simple olefins proceeds easier, the content of the product of hydrosilylation in the reaction mixture reaches 94.3%.

The influence of reagents, solvent polarity, and temperature on the etherification of chlorosilanes ClCH2SiCl3, VinSiCl3, PrSiCl3, and Ph3SiCl with ethanol was studied. Influence of reaction temperature on the ratio of the synthesized alkoxysilane and related side-product siloxane is revealed. Use of excess alcohol is shown to increase the content of siloxane. Introduction of FeCl3 does not affect the synthesis. Solvents are shown to influence the reaction rate: the rate constant increases with increasing ɛ parameter of the solvent. The rate constant of etherification of chlorosilanes with ethanol falls in the series: ClCH2SiCl3 > VinSiCl3 > PrSiCl3. An explanation of the regularities is suggested.

N-Metallation of bromoanilines with ethylmagnesium bromide followed by a reaction with trimethylchlorosilane provided N-mono and N-bis(trimethylsilyl)bromoanilines depending on the structure of substrate. The metallation of bissilylated bromoanilines with butyllithium permitted the introduction of a trimethylsilyl substituent in the aromatic ring. Previously unknown 2-bromo-N,N-bis(trimethylsilyl)aniline, 2,6-dibromo-N-trimethylsilylaniline, 2,6-dibromo-N,N-bis(trimethylsilyl)aniline, 2-bromo-6-trimethylsilylaniline, 2-bromo-6-trimethylsilyl-N,N-bis(trimethylsilyl)aniline, 2-bromo-6-trimethylsilyl-N-trimethylsilylaniline, 2,4,6-tribromo-N-trimethylsilylaniline, and 2,4,6-tribromo-N,N-bis(trimethylsilyl)aniline were prepared. The structures of the compounds obtained were established by the chromato-mass spectrometry and 1H, 13C, and 29Si NMR spectroscopy.

Hydrosilylation of allyl glycidyl ether with triethoxysilane in presence of Speier’s catalyst leads to triethoxy(3-glycidoxypropyl)silane and triethoxy(2-glycidoxy-1-methylethyl)silane and is accompanied by isomerization of allyl glycidyl ether and cleavage of the oxirane ring and the ether bond. An effect of admixtures in allyl glycidyl ether on the process is revealed. Some other hydrosilylation catalysts and additives to Speier’s catalyst are studied

Reactions of allyldiethylamine and allylbis(trimethylsiyl)amine with hexylsilane are studied. The former reaction involves hydrogen evolution and Si-Si bond formation. The contribution of hydrosilylation is insignificant. Substituent exchange between the nitrogen and silicon atoms in the silane is found. In the reaction with allylbis(trimethylsilyl)amine, no evolution of hydrogen is observed, and hydrosilylation takes place. With allyl chloride, hydrosylilation, reduction, and Si-Si bond formation are observed. Quantumchemical calculations for the reactions with diethylallylamine and allylbis(trimethylsilyl)amine were carried out at the PM3, B3LYP/6-31G**, and B3LYP/LanL2DZ levels to show that these reactions all are thermodynamically allowed, and the difference in the behavior of the amines is explained by kinetic and conformational factors.

The reaction of hexylsilane with allylamine is accompanied by the liberation of hydrogen and formation of allylaminosilanes and compounds with the Si-Si bond. The hydrosilylation pathway virtually is not realized. The B3LYP/6-311G** calculations show that all the considered reactions are thermodynamically allowed.

Hydrosilylation of ethylene with trialkoxysilanes in the presence of Pt(0) complexes as catalysts affords ethyltrialkoxysilanes in almost quantitative yields. No impurities of vinyltrialkoxysilanes were detected. Experiments and ab initio calculations showed that the Pt(0) catalysts are considerably more active in ethylene hydrosilylation than Pt(II) catalysts.

Reaction of acrylonitrile and 1,4-dicyanobut-1-ene with hydrosilanes in the presence of various catalysts was studied. In the presence of triallylamine, allyl-bis(triethoxypropyl)amine, diallylaminopropyltriethoxysilane, HMPA, NiCl2 + 2MePh2PO, CuCl + 2MePh2PO, [(Me2N)2CCl]2CuCl4, and [(Me2N)2CCl]2PtCl6, the addition of trichlorosilane to acrylonitrile proceeded with the yield of 36 to 97%. Triethoxy- and tributoxysilane were added to acrylonitrile in the presence of rhodium dicarbonyl acetylacetonate with the formation of α-isomer in 56–58% yield. Attempted addition of hydrosilanes to 1,4-dicyanobutene failed.

In the reaction of hydrochlorosilanes with methacrylamide along with addition polymerization was observed. Under the influence of hydrochlorosilanes, conjugated nitroolefines were reduced to form respective nitroso derivatives which could not be isolated due to the instability of the reaction mixtures.

Hydrosilylation of allyl esters of fluoro acids and ethers of fluoro alcohols with hydrochlorosilanes in the presence of the Speier’s catalyst was studied. Yields of adducts with ethers reach 62–68%, and with esters, 27–45%. By etherification of the adduts with ethers the respective ethoxysilanes were obtained in 41–43% yield. The latter reaction even in very mild conditions is complicated by the formation of a large amount of siloxanes. Yield of siloxanes is 22–32%.

The reactions of separate and competitive hydrosilylation of propylene with HSiCl3, MeSiHCl2, Me2SiHCl, and MePh2SiH in the presence of the Speier catalyst (SC) with different additives and a catalyst obtained from SC and propylene were studied. A mutual influence of the hydrosilanes in the competitive reactions was found. The influence of various additives to SC on the process was considered.

Hydrosilylation of several unsaturated compounds with triethoxysilane in the presence of the Speier catalyst with various additives influencing the reaction rate and selectivity was studied. The mechanism of hydrosilylation is discussed.

Bis(dialkylamino)carbenium salts {[(Me2N)2CCl]+}2MCl4 2− (M=Ni, Pd) and {[Me2NC(X)NR2]+}2PtCl6 2− (R=Me, All; X=H, Cl, Me) are efficient catalysts for hydrosilylation of allyl phenyl ether, triallylamine, allyl chloride, allylamine, and 1-octene with various hydrosilanes. The catalytic activity is dependent on the salt composition and the nature of the metal M, the saturated compound, and the hydrosilane used. The catalysts used are usually insoluble in the reaction mixture, active, and stable. In some cases, carbenium salts are more selective than Speier's catalyst. Novel catalysts, silica-immobilized dialkylaminocarbenium salts, have been prepared. The kinetics of the reaction have been considered.

Novel dialkylaminocarbenium salts with metallocomplex counter ions were prepared by the reaction of phosgene with either DMF or tetramethylurea in the presence of metal chlorides. Reactions of organosilicon amides with phosgene gave corresponding carbenium salts, while organosilicon ureas yielded aminoiminocarbenium salts. Dialkylaminochlorocarbenium salts were reduced with hydrosilanes to give dialkylaminocarbenium, salts and can be easily hydrolyzed to afford either amides or ureas. Pathways of the reaction with water and alcohols depend on the nature of reagent and the reaction conditions.

Reaction SiCl4+ Ge(OR)4 → GeCl4+ Si(OR)4 was carried out for the first time. Triethoxysilane reduces tetraethoxygermane via intermediate formation of unstable GeH(OEt)3 that transforms into GeO·Et2O or Ge(OH)2.

The kinetics of etherification of organochlorosilanes with various substituents on the silicon atom with ethanol were studied. The etherification rate is mostly controlled by the inductive constants of the substituents and increases as the electron-acceptor power of the substituents increases. The ρ* value in the Taft equation for etherification of organochlorosilanes with ethanol was determined.

Bis(dialkylamino)carbenium salts {[(Me2N)2CCl]+}2MCl4 2− (M=Ni, Pd) and {[Me2NC(X)NR2]+}2PtCl6 2− (R=Me, All; X=H, Cl, Me) are efficient catalysts for hydrosilylation of allyl phenyl ether, triallylamine, allyl chloride, allylamine, and 1-octene with various hydrosilanes. The catalytic activity is dependent on the salt composition and the nature of the metal M, the saturated compound, and the hydrosilane used. The catalysts used are usually insoluble in the reaction mixture, active, and stable. In some cases, carbenium salts are more selective than Speier's catalyst. Novel catalysts, silica-immobilized dialkylaminocarbenium salts, have been prepared. The kinetics of the reaction have been considered.

Hydrosilylation of several unsaturated compounds with triethoxysilane in the presence of the Speier catalyst with various additives influencing the reaction rate and selectivity was studied. The mechanism of hydrosilylation is discussed.