Reductive silylation probable intermediates

Silicon-carbon bonds can be prepared by reductive silylation with an active metal, a chlorosilane, and an organic substrate with electronegative substituents. Although the mechanisms have not been elucidated, organometallic intermediates are probably essential to the transformation ... 

A mechanism for catalysis by platinum compounds was proposed in 1965 by Chalk58) and has since been supported by increasing knowledge about silyl-metal systems and by the direct detection of Pt-Si211) and Rh-Si61,18s) complexes in the reaction mixtures. The suggested mechanism requires olefin coordination to the Pt(II) species (in the case of H2PtCl6 formed by reduction by the silicon hydride), oxidative addition of the silane, formation of an intermediate in which silicon and alkyl are both bonded to the platinum center, and reductive elimination of alkylsilane, probably assisted by coordination of more olefin ... 

The mechanism of the Pd-catalyzed desulfinylation of silyl sulfinate 162 into 163 has not been established yet. Probably the Pd(0) intermediate (reduction of Pd(OAc)2 by PhaP) undergoes C—S bond oxidative addition with formation of an (allyl)Pd-S02SiMe3 species that loses SO2, followed by protolysis with I -PrOH. This generates an intermediate of type (allyl)Pd-H that undergoes regio- and stereoselective (3-insertion of hydride to provide the final product. 

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