Preparative electrochemical oxidation of cyclic peralkylsilanes
作者:James Y. Becker、Elias Shakkour、Robert West
DOI:10.1016/s0040-4039(00)61166-8
日期:1992.9
The electrochemical oxidation of cyclic peralkylsilanes undergo ring opening followed by further Si-Si bond cleavage and reaction with BF4- to form alpha,omega-difluorosilanes, F-(SiR2)n-F, as major products.
Reactions of a series of peralkylcyclopolysilanes with iodine were found to proceed via second-order kinetics. Rate constants show that, in general, the smaller rings react faster than larger rings. Values of the activation parameters, Ea and ΔG\eweq, decreased with the decreasing ring size and are parallel with those of the oxidation potentials and of the lowest transition energies.
研究发现,一系列全烷基环多硅烷与碘的反应是通过二阶动力学进行的。速率常数表明,一般来说,较小的环比较大的环反应更快。活化参数 Ea 和 ΔG\eweq 的值随着环尺寸的减小而减小,与氧化电位和最低转变能的值平行。
PREPARATION OF PERALKYLCYCLOPENTASILANES, [R<sub>2</sub>Si]<sub>5</sub>
Peralkylcyclopentasilanes [R2Si]5 (where R=Et, Pr, Bu and i-Bu) were prepared by the reactions of corresponding dialkyldichlorosilanes (R2SiCl2) with lithium.