Synthesis, Characterization and Hydrolysis of Osmium Tetraphosphorus Complexes

The reaction of [CpOs(PPh(3))(2)Cl] (1) with one equivalent of white phosphorus in the presence of AgOTf (OTf = triflate, OSO(2)CF(3)) as chloride scavenger affords the stable metal complex [CpOs(PPh(3))(2)(eta(1)-P(4))]OTf (2), which contains the tetrahedral P(4) W-bound to the CpOs(PPh3)2 metal fragment. Addition of [CpRu(PPh(3))(2)(OTf)] to 2 yields the heterobimetallic species [{CpRu(PPh(3))(2)}(CpOs(PPh(3))(2)}(mu,eta(1:1)-P(4))](OTf)(2) (3), in which the tetrahedral P(4) is bound to two different metal fragments through two phosphorus atoms. The compounds have been characterized by elemental analysis, IR and NMR spectroscopy, and their crystal structures have been determined by X-ray diffraction. The coordinated P(4), at variance with the free Ligand, reacts with an excess amount of water in thf under mild conditions to yield several products, most of which have been characterized.