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• W2009569478 abstract "Abstract Time‐resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1‐chloro‐1‐silacyclopent‐3‐ene, are carried out to obtain rate constants for its bimolecular reaction with ethene, C 2 H 4 , in the gas‐phase. The reaction is studied over the pressure range 0.13–13.3 kPa (with added SF 6 ) at five temperatures in the range 296–562 K. The second order rate constants, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equation: log( k ∞ /cm 3 molecule −1 s −1 )=(−10.55±0.10) + (3.86±0.70) kJ mol −1 / RT ln10. The Arrhenius parameters correspond to a loose transition state and the rate constant at room temperature is 43 % of that for SiH 2 + C 2 H 4 , showing that the deactivating effect of Cl‐for‐H substitution in the silylene is not large. Quantum chemical calculations of the potential energy surface for this reaction at the G3MP2//B3LYP level show that, as well as 1‐chlorosilirane, ethylchlorosilylene is a viable product. The calculations reveal how the added effect of the Cl atom on the divalent state stabilisation of ClSiH influences the course of this reaction. RRKM calculations of the reaction pressure dependence suggest that ethylchlorosilylene should be the main product. The results are compared and contrasted with those of SiH 2 and SiCl 2 with C 2 H 4 ." @default.
• W2009569478 created "2016-06-24" @default.
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• W2009569478 date "2010-01-26" @default.
• W2009569478 modified "2023-10-10" @default.
• W2009569478 title "Gas-Phase Kinetics of Chlorosilylene Reactions II. ClSiH + C₂H₄: Absolute Rate Measurements and Quantum Chemical and RRKM Calculations for the Prototype π Addition Reaction" @default.
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• W2009569478 doi "https://doi.org/10.1002/cphc.200900490" @default.
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