- Reactions of diruthenium tetrahydride complex (η5-C5Me5)Ru(μ-H)4 Ru(η5-C5Me5) with vinylsilanes: Formation of a μ-silylene complex via successive Si-H and Si-C bond cleavage of dimethylvinylsilane
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The diruthenium complex {Cp*Ru(μ-H)}2{μ-η2:η2- HSiMe2(CH=CH2)} (5a; Cp* = η5-C5-Me5) containing a μ-vinylsilane ligand was prepared by the reaction of Cp*Ru(μ-H)4RuCp* (1) with dimethylvinylsilane. The μ-η2:η2-coordination mode of dimethylvinylsilane was confirmed by means of 1H, 13C, and 29Si NMR and IR spectroscopy. The Si-C(sp2) bond of 5a was readily cleaved upon thermolysis with liberating hydrogen and resulted in formation of the μ-silylene, μ-ethylidyne complex (Cp*Ru)2(μ-SiMe2)(μ-CCH3)(μ-H) (8) via the μ-sily μ-vinyl complex (Cp*Ru)2(μ-η2-HSiMe2) (μ-η2-CH=CH2) (9a) as an intermediate. The reaction of 1 with trimethylvinylsilane rendered cleavage of both Si-C(sp2) and Si-C(sp3) bonds, which resulted in formation of 8. Treatment of 8 with carbon monoxide led to formation of the μ-ethylidene complex by migration of the hydride to the bridging carbon; thus {Cp*Ru-(CO)}2(μ-CHMe)(μ-SiMe2) (10) was obtained. The reaction of 8 with ethylene afforded the μ-vinyl, μ-silylene complex (Cp*Ru)2(μ-η2-CH=CH2) (μ-SiMe2)(μ-H) (CH2=CH2) (11). The reaction of 8 with molecular hydrogen resulted in a re-formation of 1 with liberating dimethylethylsilane, which showed formation of the Si-C bond on the dinuclear system. The molecular structures of 5a, 8, and 10 were determined by single-crystal X-ray diffraction studies.
- Takao, Toshiro,Amako, Masa-Aki,Suzuki, Hiroharu
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- PROCESS FOR FUNCTIONALIZATION OF ORGANO-ZINC COMPOUNDS WITH HALOSILANES USING BASIC NITROGEN CONTAINING HETEROCYCLES AND SILYL-FUNCTIONALIZED COMPOUNDS PREPARED THEREBY
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A process to functionalize organo-zinc compounds with halosilane electrophiles employs a basic additive. The process includes combining the organo-zinc compound, a halosilanes, and a nitrogen containing heterocycle as the basic additive. The presence of the basic additive facilitates successful substitution. Functionalized silanes and silyl-terminated polyolefins can be prepared using this process. The functionalized silanes may be useful as endblockers for polyorganosiloxanes having SiH and/or silicon bonded aliphatically unsaturated groups capable of undergoing hydrosilylation.
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Paragraph 0033
(2019/10/15)
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- Ion-molecular reactions of free ethylsilicenium ions with alcohols in the gas phase
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Ion-molecular reactions of free ethylsilicenium ions with methanol and isobutanol in the gas phase were studied radiochemically. Within the reaction time the ethylsilicenium ion completely isomerizes into the dimethylsilicenium ion. The reaction mechanism was suggested.
- Kochina,Shchukin,Nefedov,Sinotova
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p. 885 - 888
(2007/10/03)
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