Arican, Haluk; Arthur, Neville L., Australian Journal of Chemistry, 1983, vol. 36, # 11, p. 2185 - 2194
作者:Arican, Haluk、Arthur, Neville L.
DOI:——
日期:——
Kinetic studies of the reaction of chlorine atoms with tetramethylsilane
作者:Yannis G. Lazarou、Panos Papagiannakopoulos
DOI:10.1021/j100128a010
日期:1993.7
The reaction Cl + (CH3)4Si --> HCI + (CH3)3SiCH2 has been studied with the very low pressure reactor (VLPR) technique in the temperature range 273-363 K. The rate constant for the forward reaction is given by the expression k = (3.58 +/- 0.76) x 10(-10) exp[(-490 +/- 240)/RT] c,3 molecule-1 s-1 (R is expressed in cal mol-1 K-1). The conventional transition-state (TS) theory indicates that the TS is bent with a Cl...H...C angle ca. 160-degrees and the Cl atom on the H...C---Si plane and inside the methyl group cone. The (CH3)3SiCH2 radical was observed as a reaction product, and it appears to be a rather stable radical due to a d-p electron delocalization.
Quantitative measure of .alpha.-silyl carbanion stabilization. The electron affinity of (trimethylsilyl)methyl radical