Reaction of O(3P) with Trimethylsilane

Article abstract of DOI:10.1021/j100259a038

The title reaction has been investigated at room temperature in a discharge flow system as well as by stationary Hg(³P₁) sensitized N2O photolysis experiments.O(³P) atoms abstract hydrogen from the silicon center with a rate constant of k(1) = (2.6 +/= 0.3)E-12 cm³s^-1.Hydroxyl radicals formed in the primary step react in a second abstraction reaction to yield H2O with a rate constant larger than k(1) by a factor of about 20.The fate of trimethylsilyl radical, the other primary product, depends on the experimental conditions.In the flow system they combine with O and OH; the combination products decompose unimolecularly, yielding CH3 and CH4, respectively, and the common product (CH3)2SiO.In stationary photolyses they mainly abstract O from N2O to ultimately form (CH3)3SiOSi(CH3)3.In a separate static experiment a ratio of k(14)/k^1/2(7) = 2.5E-12 cm^3/2s^-1/2 has been determined for oxygen abstraction of trimethylsilyl radicals from N2O vs. combination of two trimethylsilyl radicals.The rate constant of N(⁴S) with trimethylsilane has been measured in the flow system to be k(2) = (2.6 +/= 0.8)E-14 cm³s^-1.