Abstract
Ruthenium complexes such as RuHCl(CO)(PPh3)3 (I), RuCl(SiMe3)(CO)(PPh3)2 (II), RuCl2(PPh3)3 (III), and Ru(CO)3(PPh3)2 (IV) appear to be very effective catalysts of cross-disproportionation of vinyl-trisubstituted silanes CH2CHSiR3 (where R3 = Me3, PhMe2, (OEt)3) with vinyl alkyl ethers CH2CHOR‘ (where R‘ = ethyl, n-propyl, n-butyl, tert-butyl, tert-pentyl, 2-ethylhexyl, cyclohexyl, trimethylsilyl) to yield a mixture (E+Z) of 1-silyl-2-alkoxyethenes. Stoichiometric insertion of vinyl n-propyl ether into Ru−Si bonds of II and MS study of the products of the deuterated vinyltrimethylsilane with vinyl ethyl ether indicate that the mechanism of cross-disproportionation involves a migratory insertion of the vinyl ether into the Ru−Si bond (and vinylsilane into the Ru−H bond) followed by β-H (and β-Si) transfer to eliminate 1-triorganosilyl-2-alkoxyethenes (and ethene).
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