Silicon hydrides and nickel complexes

Hydrosilylation of CC and CC

“…(4) + As a model of the oxidative addition product, a platinum(O) complex (8) has been found to afford an isolable platinum(II) compex (9), which has a Si-Pt-H bond. 18 / CY3P -Pt( 8) Cy =cyclohexyl (9) The stereochemistry of the oxidative addition has been studied using optically active I-naphthyl(methyl)phenylsilane (11) and its deuterium derivative (10). The HID exchange reaction of the hydrosilane proceeds with 100% retention of configuration (equation 5).…”

“…1b In the presence of a heterogeneous catalyst like Pd/'yalumina, Rh/carbon and polymer bound Pt, trichlorosilane gives trichlorovinylsilane with atmospheric pressure of acetylene. 1b Platinum supported on sulfur-containing silica gel is a practical catalyst for 1,2dihydrosilylation, as exemplified in equation (10) (10) Thermal hydrosilylation of acetylene is feasible, but requires a high reaction temperature. A rather unusual example is shown in equation (11).27 590°C 30% ( 11) Hydrosilylation of acetylene with bifunctional hydrosilanes, e.g.…”

Catalytic C−C Bond Formation through Selective Activation of C−F Bonds

“…[8] The usefulness of cross-coupling chemistry to form unsymmetrical biaryls has been demonstrated and the interest in catalytic cross-coupling chemistry has undoubtedly been driven by the development of catalyst systems that have successively allowed the activation of aryl iodides, bromides, and finally chlorides even at ambient temperature. [10] Based on general considerations, we therefore developed a strategy for the application of aryl fluorides in cross-coupling reactions: Kinetically, the catalyst must be able to 1) chemoselectively activate the aryl fluoride but still allow 2) the completion of the catalytic cycle by reductive elimination and CÀC bond formation. Only the coupling of an sp 3with an sp 2carbon center, as exemplified in the reaction of fluorobenzene with isopropylmagnesium chloride mediated by [Ni(dmpe)-Cl 2 ] (dmpe 1,2-bis(dimethylphosphanyl)ethane), has been reported.…”

The Oligomerization of Olefins and Related Reactions

“…The reactivity of the silanes with 1-octene decreases in the order HSiCl 3 > HSiCl 2 CH 3 > HSiCl(CH 3 ) 2 » HSi(CH 3 ) 3 and the reaction is confined to the hydrosilylation of terminal or cyclic olefins (302). The direction of addition depends to some extent on the nature of the modifying ligand.…”