Oxidation of Triorganosilanes and Related Compounds by Chlorine Dioxide

Oxidation of triethylsilane, tert-butyldimethylsilane, dimethylphenylsilane, triphenylsilane, 1,1,1,2tetramethyl-2-phenyldisilane, tris(trimethylsilyl)silane, hexamethyldisilane, tetrakis(trimethylsilyl)silane, 1,1,3,3tetraisopropyldisiloxane with chlorine dioxide was carried out. The reaction products of studied triorganosilanes with chlorine dioxide in an acetonitrile solution were the corresponding silanols and siloxanes. A mechanism explaining the formation of products and the observed regularities of the oxidation of silanes with chlorine dioxide has been proposed. A thermochemical analysis of some possible pathways in the gas phase using methods G4, G3, M05, and in an acetonitrile solution by the SMD-M05 method was carried out. The oxidation process can occur both with the participation of ionic and radical intermediates, depending on the structure of the oxidized substrate and medium.