Thiolate complexes of osmium(IV): preparation of [Os(SR)4(PR′3)](R = C6F5, C6F4H-4, C6H4F-4 or Ph, R′= Ph; R = C6F5 or C6F4H-4, R′3= Me2Ph) and [OsCl(SC6F5)2(SC6H4X-3)(PMe2Ph)](X = F or CF3): crystal structures of [Os(SC6F4H-4)4(PPh3)] and [OsCl(SC6F5)2(SC6H4CF3-3)(PMe2Ph)]

Abstract

The diamagnetic osmium(IV) complexes [Os(SR)₄(PR′₃)](R = C₆F₅, C₆F₄H-4, C₆H₄F-4, or Ph, R′= Ph; R = C₆F₅ or C₆F₄H-4, R′₃= Me₂Ph) and [OsCl(SC₆F₅)₂(SC₆H₄X-3)(PMe₂Ph)](X = F or CF₃) have been prepared. The complex [Os(SC₆F₄H-4)₄(PPh₃)] has an essentially trigonal-bipyramidal structure with an apical PPh₃ group [Os–P 2.391 (5), Os–S_ap 2.414(5), mean Os–S_eq, 2.207(7)Å]. The structure of [OsCl(SC₆F₅)₂(SC₆H₄CF₃-3)(PMe₂Ph)] is a somewhat distorted triagonal bipyramid with apical Cl^– and PMe₂Ph groups [Os–Cl 2.420(2), Os–P 2.340(2), mean Os–SC₆F₅ 2.206(2), Os–SC₆H₄CF₃2.187(2)Å]. The spectroscopic properties of these compounds are reported and the possibility of isomerism in solution is discussed.