Synthesis and characterization of the osmium compound cis(CO)-ClOs(CO)(2)(bpcd)[C(O)Et]

摘要

Photochemical activation of the triosmium cluster Os-3(CO)(12) in CH2Cl2 solvent and ethylene, followed by treatment with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd), furnishes the new octahedral compound cis(CO)-ClOs(CO)(2)(bpcd)[C(O)Et] in low yield. The title compound has been isolated and characterized in solution by IR and H-1 NMR spectroscopies, with the solid-state structure of cis(CO)-ClOs(CO)(2)(bpcd)[C(O)Et] determined by X-ray diffraction analysis. cis(CO)-ClOs(CO)(2)(bpcd)[C(O)Et] crystallizes in the triclinic space group P-1, a = 10.043(2), b = 11.455(2), c = 16.221(3) angstrom, alpha = 74.900(3)angstrom, beta = 76.150(3)angstrom, gamma = 76.221(2)angstrom, V = 1718.2(5) angstrom(3), Z = 2, D-cacl = 1.717 Mg/m(3); R = 0.0453, R-w = 0.0778 for 6703 observed reflections with I > 2 sigma(I). The presence of the chlorine and propanioyl groups in cis(CO)-ClOs(CO)(2)(bpcd)[C(O)Et] is structurally confirmed, and the origin of the these groups from the reaction solvent and ethylene is discussed.