Mechanism of thermolysis of tetramethylsilane and trimethylsilane

Abstract

The thermolysis of tetramethylsilane has been studied in a pulsed stirred-flow system between 840 and 1055 K, yielding significantly different Arrhenius parameters above and below 950 K. The high temperature results relate to a non-chain mechanism, whence D(Me₃Si–Me)= 355 ± 6 kJ mol^–1 while the low temperature results relate to a short chain sequence. A mechanism for the latter is shown by computer-aided numerical integration to be consistent with experimental results, as is a similar chain mechanism for the thermolysis of trimethylsilane.