Silane complexes overview

A. Silane a-Complexes. A Short Historical Overview of Benchmark Results.. 219... 

Summary Two catalytic reactions, i.e. silylative coupling (mms-silylation) (SC) catalyzed by complexes containing or generating Ru-H and/or Ru-Si bonds (I, II, V, VI) and cross-metathesis (CM) catalyzed by mthenium-carbene (i.e. 1st and 2nd generation mthenium Grubbs catalyst (ID, IV)) of vinyl and allyl-substituted hetero(N,S,B)organic compounds with conunercially available vinyltrisubstituted silanes, siloxanes, and silsesquioxane have been overviewed. They provide a universal route toward the synthesis of well-defined molecular compounds with vinylsilicon functionality. 

Silanes bearing Si—H bonds are of basic interest in catalytic reactions. Transition metals or transition metal complexes, respectively, are able to catalyze hydrosilylation which is a useful approach to polysilanes. The major drawback of this method is the relatively low molecular weight of the polysilanes generated. The reaction pathway, as well as the reaction products, depend on the nature of the educts and particularly on the catalyst which is used. Numerous transition metals can be effective catalysts either as metal or in compounds. For a general overview some key reactions of transition metal catalysts are given in Scheme 5. The hydrosilylmetal species (a), which is... 

Much work has also been conducted on the hydrosilylation of ketones and imines (Equation 16.16). The products from these reactions are silyl ethers and sdylamines. These additions of silanes across C-X ir-bonds have been conducted predominantly for the purpose of generating optically active alcohols and amines after hydrolysis. Because the mechanism of these reactions is less defined than the mechanism of alkene hydrosilylation, and this chemistry lies outside the theme of this chapter, the hydrosilylation of ketones and imines is presented only briefly. Instead, this chapter provides an overview of the scope and motivation for the hydrosilylation of alkenes and alkynes and provides details on the mechanisms of these reactions catalyzed by complexes of various metals. Several comprehensive reviews of the scope of these reactions have been published. ... 

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