Abstract
The reaction of triorganosilanes with aryldisulfides yielding triorgano(arylthio)silanes and thiophenols has been studied at 180–209°C by kinetic methods. The overall reaction order and pseudo-order reaction rate constants for systems R3SiH/(p-FC6H4S)2 and (ArS)2/PhEt2SiH have been determined. A free radical chain mechanism with thermal dissociation of aryldisulfide as initiation step is proposed. The reactivities of triorganosilanes in reactions with disulfides follow the same reactivity series as reported previously for the reaction of triorganosilanes with elemental sulfur.

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