Silicon: Organosilicon Chemistry

Abstract An overview of the chemistry of organosilicon compounds from the first synthesis in 1863 to the latest results is presented. After an introduction, classes of compounds and nomenclature are briefly described. Synthesis of organosilicon compounds is then disucssed systematically. Characteristic points of structure and bonding of organosilicon compounds, including tetrahedral and polyhedral compounds are described. Important σ–π conjugation (sigma‐pi conjugation) and σ*–π conjugation (sigma*‐pi conjugation) in organosilicon compounds are discussed in relation to structure and reactions. Reactions of organosilicon compounds are classifed into ionic and hemolytic (nonionic) reactions and various reactive intermediates including silyl radicals, silylium ions (silyl cations), silyl anions, and silylenes are described. Recent developments in kinetic stablization of these reactive intermediates are then summarized. In relation to kinetic stablization, silicon‐containing multiple bonds, silaaromatics, and silicon polyhedranes are described. Lastly, two important applications of organosilicon compounds, namely polymers and organic synthesis, are described briefly.