A New Series of Mono- and Dinuclear Hydridosilylrhodium(III) Complexes, RhCl(H)(SiAr3)L2and RhL(SiAr3)H(μ-Cl)(μ-H)RhH(SiAr3)L (L = P(i-Pr3)). Preparation by Oxidative Addition of HSiAr3and Molecular Structures of the Complexes

Abstract

Reactions of triarylsilanes such as HSiPh3, HSi(C6H4Me-p)3, HSi(C6H4OMe-p)3, HSi(C6H4Cl-p)3, HSi(C6H4F-p)3, and HSi(C6H4CF3-p)3 with RhClL2 (L = P(i-Pr)3) give a series of hydrido(triarylsilyl)rhodium(III) complexes, RhCl(H)(SiAr3)L2 (1, Ar = Ph; 2, Ar = C6H4Me-p; 3, Ar = C6H4OMe-p; 4, Ar = C6H4Cl-p; 5, Ar = C6H4F-p; 6, Ar = C6H4CF3-p). Tris(phenylethynyl)silane also reacts with the Rh(I) complex to give another oxidative-addition product, RhCl(H)[Si(C⋮CPh)3]L2 (7). X-ray analyses of 1 and 7 show a distorted-square-pyramidal coordination around the Rh center with the silyl ligand at the apical position. Prolonged reactions of HSiPh3 and of HSi(C6H4OCF3-p)3 with RhClL2 give dinuclear complexes, RhL(SiAr3)H(μ-Cl)(μ-H)RhH(SiAr3)L (8, Ar = Ph; 9, Ar = C6H4OCF3-p). X-ray crystallography of 9 shows a molecular structure containing two Rh centers bridged with hydrido and chloro ligands. 1,1,3,3-Tetraisopropyldisiloxane undergoes oxidative addition of the SiH bonds to RhClL2 to give a symmetric dinuclear Rh(III) ...