We studied the reactivity of an osmium vinyl complex containing a coordinated hydroxyl group OsCl2(PPh3)2[CH= C(PPh3)-CHPh(OH)] (1) toward bidentate ligand 1,4- bis(diphenylphosphino)butane (DPPB), π acid ligand (CO), base (Cs 2CO3) and heat. Two osmium vinyl complexes OsCl 2(dppb)[CH=C(PPh3)CHPh(OH)] (2) and OsCl 2(CO)2(PPh3)[CH=C(PPh3)CHPh(OH)] (3), as well as two relatively rare phosphonium-containing osmafuran complexes Os(η2-OCOO)(PPh3)2[CHC(PPh 3)CPhO] (4) and OsCl2(PPh3) 2[CHC(PPh3)CPhO] (5), were obtained in high yields from these reactions. All products were characterized by NMR spectroscopy, elemental analysis, and their structures were further confirmed by single crystal X-ray diffraction. ? 2013 Science China Press and Springer-Verlag Berlin Heidelberg