Journal of the Chemical Society - Faraday Transactions p. 27 - 34 (1990)
Update date:2022-08-11
Topics:
Baggott, James E.
Frey, H. Monty
Lightfoot, Phillip D.
Walsh, Robin
Watts, Ivy M.
Absolute rate constants for reactions of silylene have been determined by time-resolved measurements of its decay at room temperature, following formation by pulsed-laser photolysis of phenylsilane in the presence of various added silanes.For SiH4 and Si2H6 the rate coefficients are pressure dependent and the former reaction is succesfully modelled using RRKM theory.High-pressure (or pressure-independent) rate constants (in 10-10 cm3 molecule-1 s-1) are: SiH4, ca. 4.0; Si2H6, ca. 6.5; MeSiH3, 3.66 +/- 0.22; Me2SiH2, 3.31 +/- 0.26; Me3SiH, 2.47 +/- 0.14.Theseresults are compared with other determinations and the rate constants for the analogous reactions of SiMe2.A model for the insertion reaction is proposed in which the nucleophilic stage of the process plays an important role.
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