aFUTHER STUDIES ON REACTIONS OF ORGANIC HALIDES WITH DISILANES CATALYSED BY TRANSITION METAL COMPLEXES

Article abstract of DOI:10.1016/S0022-328X(00)86833-3

The interaction of a range of organic halides with (Cl3Si)2 or (Me3Si)2 in the presence of a variety of transition metal catalysts (very predominantly Pd⁰ or Pd^II complexes) have been examined.PhSiMe3 was formed from PhCl (m.y. = maximum yield), PhBr (m.y., 92percent, with as catalyst (L=PPh3)), and (contrary to earlier reports) PhI (m.y. 51percent, with ).MeSiCl3 was formed from MeBr (m.y., 78percent with ) and MeI (m.y., 91percent with ), and EtSiCl3 from EtBr (m.y., 49percent, with ; L''=P(C6H4OMe-p)3) and EtI (m.y. 45percent, with ).Me4Si was satisfactorily formed from MeBr (m.y. 42percent, with ).Evidence was obtained for the formation of Me3SiCF3 from CF3I.Very poor yields of XC6H4CH2SiMe3 were obtained from XC6H4CH2Br (X=H or p-Me) (with X=H some PhSiMe3 was formed), but p-O2NC6H4CH2SiMe3 was formed in 48percent yield from p-O2NC6H4CH2Cl with as catalyst.PhCOSiMe3 was formed from PhCOCl (m.y. 52percent with ).The nickel complex was moderately effective as a catalyst for reactions between (Cl3Si)2 and MeBr, EtBr, or PhCH2Br.The new complex was prepared by treatment of with (Cl3Si)2 or Cl3SiH, and shown to catalyse the reaction between MeBr and (Cl3Si)2.