A late-transition metal oxo complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9- |
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Authors: | Anderson Travis M Neiwert Wade A Kirk Martin L Piccoli Paula M B Schultz Arthur J Koetzle Thomas F Musaev Djamaladdin G Morokuma Keiji Cao Rui Hill Craig L |
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Institution: | Department of Chemistry, Emory University, Atlanta, GA 30322, USA. |
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Abstract: | Terminal mono-oxo complexes of the late transition metal elements have long been considered too unstable to synthesize because of repulsion between the oxygen electrons and the mostly filled metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9O=Pt(H2O)L2], L = PW9O34(9-)], has now been prepared and isolated at room temperature as air-stable brown crystals. X-ray and neutron diffraction at 30 kelvin revealed a very short 1.720(18) angstrom] Pt-O bond and no evidence of a hydrogen atom at the terminal oxygen, ruling out a better precedented Pt-OH complex. Density functional theory and spectroscopic data account for the stability of the Pt(IV)-oxo unit by electron withdrawal into delocalized orbitals of the polytungstates. |
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