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

• Published in: Chemical physics letters Vol. 413; no. 1; pp. 194 - 200
• Main Authors: Becerra, R., Boganov, S.E., Egorov, M.P., Krylova, I.V., Nefedov, O.M., Walsh, R.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-09-2005
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2005.07.079

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 C
2H
4, CH
2
CHCMe
3, C
2H
2, Me
2O, SO
2, HCl, MeSiH
3, Me
2SiH
2, Me
3SiH, MeGeH
3, Me
2GeH
2 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 SiH
2 and SiCl
2. Relative reactivities of ClSiH and SiH
2 vary considerably.