Journal
SCIENCE
Volume 306, Issue 5704, Pages 2074-2077Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1104696
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- NIGMS NIH HHS [GM-057378] Funding Source: Medline
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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 fitted metal d orbitals. A platinum(IV)-oxo compound flanked by two polytungstate ligands, K7Na9[O=Pt(H2O)L-2], 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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