Poly(hydrosilane)s obtained by dehydrocoupling of the corresponding RSiH3 were found to be air sensitive. Analyses based on GPC, IR, and heterocorrelated 1H−29Si NMR indicate the formation of some siloxane-type structures on the polymer backbone. Kinetic studies carried out by EPR spectroscopy using fusinite as a paramagnetic probe of the oxygen concentration allowed the oxidizability of some polysilanes to be obtained. Oxidizability values of 1.2 × 10-2 and 1.8 × 10-2 M-1/2 s-1/2 were found for poly(n-hexylsilane) and poly(phenylsilane), respectively. Model studies on the oxidation of (Me3Si)2Si(H)Me with a mixture of 16O2 and 18O2 suggest that the main reaction path proceeds via a free-radical chain mechanism and involves either two or three consecutive, unimolecular steps. Poly(hydrosilane)s react with nitroxides (TEMPO) under free-radical conditions and in the absence of molecular oxygen to give the corresponding amine in good yields.

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