Synthesis and analysis of pentacoordinated and hexacoordinated osmium and ruthenium compounds

Recently we have published [M. Arroyo et nl., J. Organomet. Chem. 599 (2000 ) 170] the first results of this project about the thermolysis reactions of [Os(SR)(3)(PMe2Ph)(2)], R=C6F5 (complex la) or C6F4H-4 (complex Ib) in ref luxing toluene. These reactions afford [Os(SC6F5)(2)(o-S2C6F4)(PMe2Ph)] 2a and [Os(C6F5)(2)(o-S2C6F4)(PMe2Ph)(2)] 3a from la or [Os(SC6F4H-4)(2)(o-S2C 6F3H)(PMe2Ph)] 2b from Ib, through processes involving C-F and C-S cleavage as well as rearrangement of C-S bonds. The single crystal diffraction stru ctures of la, 2a and 3a have been determined. In the solid state compound l a shows a C-F-Os interaction. NMR H-1, P-31{H-1} and F-19 structural studie s in solution were also carried out. To analyse the thermolysis reaction va rying the basicity of the phosphine ligand, the relation thiolate:phosphine and the oxidation state of osmium atom we have already prepared the new pe ntacoordinated polifluorobenzothiolate-osmium complexes, [Os(SC6F5)(4)(P(C6 H4X-4)(3)) ] (X = OCH3, CH3, F, Cl, or CF3).