Direct detection of chlorosilylene and time resolved study of some of its reactions in the gas-phase using a new photochemical precursor

Chlorosilylene, ClSiH, was prepared by 193 nm laser flash photolysis of 1-chloro-1-silacyclopent-3-ene in the gas phase. ClSiH was monitored in real time at 457.9 nm using a CW argon ion laser. The kinetics of reactions of ClSiH with C2H4, CH2CHCMe3, C2H2, Me2O, SO2, HCl, MeSiH3, Me2SiH2, Me3SiH, MeGeH3, Me2GeH2 and precursor have been studied at ambient temperatures for the first time. Addition reactions of ClSiH and reactions with lone pair donors are faster than insertion reactions. Surprisingly ClSiH inserts faster into Si–H than Ge–H bonds. ClSiH is intermediate in reactivity between SiH2 and SiCl2. Relative reactivities of ClSiH and SiH2 vary considerably.