Organosilicon compounds. Part L. Kinetics of the thermal decomposition of bis(trimethylsilyl)mercury in solution

Abstract

The thermal decomposition of solutions of bis(trimethylsilyl)mercury in benzene or cyclohexane shows second-order kinetics, except that a small first-order contribution appears at very low concentrations in cyclohexane. In toluene mixed second- and (pseudo)-first-order kinetics are observed, and in anisole, (pseudo)-first-order kinetics only. Bis(trimethylsilyl)mercury appears to decompose mainly by bimolecular reactions, either with itself or with the solvent, with unimolecular homolysis seemingly unimportant. From the small first-order contribution to the reaction in cyclohexane, a rough lower limit of 200 kJ mol^–1 for D(Me₃Si–HgSiMe₃) can be derived.