THE REACTIONS OF HYDROSILANES WITH TRIFLUOROPROPENE AND PENTAFLUOROSTYRENE CATALYZED BY RUTHENIUM, RHODIUM AND PALLADIUM COMPLEXES

Article abstract of DOI:10.1016/S0022-328X(00)99483-X

The reactions of hydrosilanes with trifluoropropene (TFP) and pentafluorostyrene (PFS) catalyzed by Ru3(CO)12 or RhCl(PPh3)3 give β-R_f-vinylsilane (1) and/or β-R_f-ethylsilane (2) (R_f=perfluorocarbon group).The 1/2 ratio is highly dependent on the nature of hydrosilane used.The ruthenium catalyst favors the formation of 1 compared with the rhodium catalyst.Neither α-R_f-vinylsilane nor α-R_f-ethylsilane was formed at all.Possible mechanisms which can accommodate characteristic features of these reactions are discussed.The hydrosilylation of TFP with dichloromethylsilane catalyzed by PdCl2(PhCN)2/2PPh3 gives the α-adduct (9a) exclusively, and this is transformed to the corresponding dialkoxysilanes, silane diol, oligosilane diols and cyclic oligosiloxanes.