Dehalogenation of Hexachlorocyclohexanes and Simultaneous Chlorination of Triethylsilane Catalyzed by Rhodium and Ruthenium Complexes

Abstract

Complexes RhCl(PPh3)3 and RhH2Cl(PiPr3)2 catalyze the dehalogenation of γ-hexachlorocyclohexane to benzene and the simultaneous chlorination of HSiEt3 to ClSiEt3. In the presence of RhCl(PPh3)3, the dehalogenation is inhibited by addition of PPh3. 1H and 31P{1H} NMR spectroscopy studies at variable temperature, on the behavior of the complex RhCl(PPh3)3 in the presence of γ-hexachlorocyclohexane and/or HSiEt3, indicate that the catalytic reaction involves the initial interaction of the catalyst with the silane and that chloro−hydride intermediates related to RhH2Cl(PPh3)3 are the main species during the catalysis. The complexes RuHCl(PPh3)3, RuH2Cl2(PiPr3)2, and RuHCl(η2-H2)(PiPr3)2 also catalyze the dehalogenation of γ-hexachlorocyclohexane and the simultaneous chlorination of HSiEt3 to ClSiEt3. In these cases, the dehalogenation products are 6/4 cyclohexene/cyclohexane (RuHCl(PPh3)3) and 4/6 cyclohexene/benzene (RuH2Cl2(PiPr3)2 and RuHCl(η2-H2)(PiPr3)2) mixtures. The dehalogenations of α- and δ-hexachlo...