RuCl 3 · n H 2 O in MeCN catalyzes the hydrosilylation of carbon dioxide with n -Hex 3 SiH into n -Hex 3 SiOOCH and, with Me 2 PhSiH, into Me 2 PhSiOOCH. The initial catalyst formed is trans -[Ru II Cl(MeCN) 5 ][Ru III Cl 4 (MeCN) 2 ], the synthesis and structural characterization of which are described. With [Ru II Cl(MeCN) 5 ][Ru III Cl 4 (MeCN) 2 ] as a catalyst, Me 2 PhSiOOCH is produced at 313 K. Analogously, Et 2 SiH 2, Ph 2 SiH 2, and p -C 6 H 4 -(Me 2 SiH) 2 yield Et 2 Si(OOCH) 2, Ph 2 Si(OOCH) 2, and p -C 6 H 4 -(Me 2 SiOOCH) 2, respectively. When exposed to air, the latter compounds hydrolyze spontaneously into mixtures of silanediols, linear siloxane oligomers and polymers, and cyclic siloxane oligomers with the release of formic acid.
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Jansen et al. (1999) studied this question.
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