Formation of Silylgermane by a Silylene Insertion Reaction in the Infrared Photochemistry of Monosilane-Monogermane Mixtures

Article abstract of DOI:10.1021/j100271a007

The infrared photodecomposition at 944.2 cm^-1 of silane-germane mixtures has been studied over a pressure range of 24-26 torr and over a temperature range of 295-356 K.The products observed are hydrogen, disilane, silylgermane, trace amounts of trisilane, and solid polymeric material.Digermane formation was not observed.The primary photodecomposition of SiH4 is to SiH2 + H2; this is followed by insertion of SiH2 into an Si-H bond of SiH4 or a Ge-H bond of GeH4 to form Si2H6 or SiH3GeH3, respectively.On the basis of our studies of the competitive rates of SiH3GeH3 and Si2H6 formation as a function of temperature, and those in the literature relative to the absolute rate of insertion of SiH2 into SiH4, we derive the value k₂=10^10.4+/-0.5 exp<-10.7 +/- 5.3 x 10³ J/RT> L mol^-1 s^-1 for the specific reaction rate of insertion of SiH2 into a Ge-H bond of germane.