Hydrosilylation

Abstract

The article provides a comprehensive account of the research on synthetic and catalytic aspects of hydrosilylation. Reactions proceeding in the presence of nucleophilic‐electrophilic catalysts, metals and immobilized metals as well as radical initiators are described. However, particular attention is paid to processes catalysed by transition metal complexes. For these catalytic systems, mechanistic pathways and development of efficient and selective catalytic systems are more comprehensively discussed. Possible applications of hydrosilylation of multiple carbon‐carbon and carbon‐heteroatom bonds in organic and asymmetric synthesis are presented. The article summarizes applications of the hydrosilylation processes in polymer and material chemistry including their contribution in polysiloxane curing, synthesis of new hybrid materials, dendrimers and functionalized molecular and macromolecular organosilicon derivatives.

Catalysis of Hydrosilylation by Well‐Defined Surface Rhodium Siloxide Phosphine Complexes

“…[12] These results indicate that the catalytic cycle for hydrosilylation by 1 must be different from that for the respective homogeneous complex and should involve a catalytic pathway protecting the surface-siloxide intermediates against leaching throughout the whole cycle. In a similar manner to hydrosilylation by the immobilized non-phosphine rhodium siloxide complex, [12] the reaction occurred by the Chalk-Harrod mechanism, [14] (Scheme 6). However, in the case of rhodium siloxide phosphine complexes 1-3, the first step involved either dissociation, or oxygenation in the presence of oxygen, of phosphine to form complex 4, thus opening the hydrosilyla-tion catalytic cycle (Scheme 6; 1!4!5 and/or 1!4!5') or the prior oxidative addition of silicon hydride followed by phosphine dissociation (Scheme 6; 1!4'!5).…”

Synthesis of Dialkenyl-Substituted Double-Decker Silsesquioxanes as Precursors for Linear Copolymeric Systems

“…Hex-5-enyl-and dec-9-enyl-chlorosilanes we obtained via [Pt 2 (dvs) 3 ] catalyzed hydrosilylation of 1,5-hexadiene and 1,9-decadiene by Cl 2 SiMeH [14]. The reactions were carried out at room temperature and in the excess of the corresponding diene that served as the reagent and reaction medium (due to ease of isolation procedure).…”

Novel organosilicon dendrons as effective linkers for biomolecules binding on a glass surface

“…This methodology is mostly used for the synthesis of silicon-containing dendrimers, predominantly carbosilanes, carbosiloxanes and carbosilazanes, and also dendritic polysilanes and polysiloxanes. [19] Nevertheless, to the best of our knowledge, no example of a method for the synthesis of ethoxy-substituted silicon dendrons containing epoxide or amine functional groups for silica or glass surface modification has been reported so far.…”