The insertion reaction of germylene into the Si–H bond of silane: absolute rate constants, temperature dependence, RRKM modelling, and quantum chemical (ab initio and DFT) calculations

Abstract

Time resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4-dimethylgermacyclopentene-3, have been carried out to obtain rate constants for its bimolecular reaction with monosilane, SiH4. The reaction was studied in the gas-phase over the pressure range 1–100 Torr, with SF6 as bath gas, at 5 temperatures in the range 295–554 K. The reaction shows the characteristic pressure dependence of a third-body assisted association reaction. The high pressure rate constants, obtained by extrapolation, gave the Arrhenius equation: