PREPARATION AND ELECTROCHEMISTRY OF THIOLATE-PHOSPHINE COMPLEXES OF OSMIUM

The paramagnetic, octrahedral complexes [Os(SC6F5)(2)(O(2)CR)(PMe(2)Ph )(2)] (R = C6F5, 1; C6H4CF3-2, 2; C6H4CF3-(3), 3; C6H4CF3-4, 4; C6H4F- 2, 5; C6H4F-3, 6; C6H4F-4, 7; CH3, 8; CF3, 9) have been prepared by tr eatment of the penta-coordinated complex [Os(SC6F5)(3)(PMe(2)Ph)(2)] w ith the corresponding fluoro-carboxylic acid. The diamagnetic, pentaco ordinate, osmium(IV) complexes [OsX(SR)(3)(Pr-3(1))][X = Cl, Br or SR; R = C6F4H-4 or C6F5; PR(3)(1) = PMe(2)Ph, PPh(3), P(C6H4Y-4)(3) (Y = F, OMe, CF3, Me or Cl)] (10-14, 18, 20-23), show two successive one-el ectron reductions. Electrochemical data are also given for [Os(SC6F5)( 3)(PMe(2)Ph)(2)] (19). Crown Copyright (C) 1996 Elsevier Science Ltd