A Late-Transition Metal Oxo Complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9-

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Science  17 Dec 2004:
Vol. 306, Issue 5704, pp. 2074-2077
DOI: 10.1126/science.1104696

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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, K7Na9[O=Pt(H2O)L2], L = [PW9O349–], 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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