Reaction of silylene with sulfur dioxide: some gas-phase kinetic and theoretical studies

Abstract

Time-resolved kinetic studies of the reaction of silylene, SiH₂, with SO₂ have been carried out in the gas phase over the temperature range 297–609 K, using laser flash photolysis to generate and monitor SiH₂. The second order rate coefficients at 1.3 kPa (SF₆ bath gas) fitted the Arrhenius equation: log(k/cm³ molecule⁻¹ s⁻¹) = (−10.10 ± 0.06) + (3.46 ± 0.45 kJ mol⁻¹)/RT ln 10 where the uncertainties are single standard deviations. The collisional efficiency is 71% at 298 K, and in kinetic terms the reaction most resembles those of SiH₂ with CH₃CHO and (CH₃)₂CO. Quantum chemical calculations at the G3 level suggest a mechanism occurring via addition of SiH₂ to one of the SO double bonds leading to formation of the three-membered ring, thione-siloxirane which has a low energy barrier to ring expansion to yield the four-membered ring, 3-thia-2,4-dioxasiletane, the lowest energy adduct found on the potential energy (PE) surface. RRKM calculations, however, show that, if formed, this molecule would only be partially stabilised under the reaction conditions and the rate coefficients would be pressure dependent, in contrast with experimental findings. The G3 calculations reveal the complexity of possible intermediates and end products and taken together with the RRKM calculations indicate the most likely end products to be H₂SiO + SO (³Σ⁻). The reaction is compared and contrasted with that of SiH₂ + CO₂.