Abstract
Product and kinetic data on the copyrolysis of silane with ammonia and of silane with dimethylamine are reported. The main products of the SiH4/NH3 reaction are disilane and silylamine, and the main products of the SiH4/Me2NH reaction are Si2H6 and Me2NSiH3. The silylamine products are produced by SiH2 insertions into the N−H bonds of the amine reactants, and rate constants for this insertion lie in the k2 ∼ 2 × 109 M-1 s-1 range, with no temperature dependence within the errors. Kinetic and product data on the pyrolysis of dimethysilylamine are also presented. Reactant loss followed reasonable first-order kinetics and produced rate constants consistent with Arrhenius parameters of log A(sec-1) = 12.64 ± 0.98 and E = 48.02 ± 3.1 kcal/mol. A mechanism of reaction, based on the kinds of silylene intermediate reactions expected, is presented. Comparisons of mechanistic expectations with the product data, however, indicate a more complex reaction system.
Published Version
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