Thiolate complexes of osmium(III) and osmium(IV). Crystal structures of [Os(SC6F5)2(O2CPh)(PMe2Ph)2] and [OsCl-(SC6F5)3(PMe2Ph)]

Abstract

Treatment of [Os(SR)₃(PMe₂Ph)₂](R = C₆F₅ or C₆HF₄) with PhCO₂H or with HCl in acetone gives, respectively, the red paramagnetic osmium(III) derivatives [Os(SR)₂(O₂CPh)(PMe₂Ph)₂]1 and the green, five-co-ordinate, diamagnetic osmium(IV) complexes [OsCl(SR)₃(PMe₂Ph)]2. X-Ray crystallography has shown that 1(R = C₆F₅) has an octahedral structure with trans-thiolates, cis-phosphines and a chelating benzoate ligand and that 2(R = C₆F₅) has a trigonal-bipyramidal structure with thiolates in the equatorial plane.