Revisiting the Polyoxometalate-Based Late-Transition-Metal-Oxo Complexes: The 鈥淥xo Wall鈥?Stands

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• 作者：Kevin P. O鈥橦alloran ; Chongchao Zhao ; Nicole S. Ando ; Arthur J. Schultz ; Thomas F. Koetzle ; Paula M. B. Piccoli ; Britt Hedman ; Keith O. Hodgson ; Elena Bobyr ; Martin L. Kirk ; Sushilla Knottenbelt ; Ezra C. Depperman ; Benjamin Stein ; Travis M. Anderson ; Rui Cao ; Yurii V. Geletii ; Kenneth I. Hardcastle ; Djamaladdin G. Musaev ; Wade A. Neiwert ; Xikui Fang ; Keiji Morokuma ; Shaoxiong Wu ; Paul K枚gerler ; Craig L. Hill
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：July 2, 2012
• 年：2012
• 卷：51
• 期：13
• 页码：7025-7031
• 全文大小：331K
• 年卷期：v.51,no.13(July 2, 2012)
• ISSN：1520-510X

文摘

Terminal oxo complexes of the late transition metals Pt, Pd, and Au have been reported by us in Science and Journal of the American Chemical Society. Despite thoroughness in characterizing these complexes (multiple independent structural methods and up to 17 analytical methods in one case), we have continued to study these structures. Initial work on these systems was motivated by structural data from X-ray crystallography and neutron diffraction and ¹⁷O and ³¹P NMR signatures which all indicated differences from all previously published compounds. With significant new data, we now revisit these studies. New X-ray crystal structures of previously reported complexes K₁₄[P₂W₁₉O₆₉(OH₂)] and 鈥淜₁₀Na₃[Pd^IV(O)(OH)WO(OH₂)(PW₉O₃₄)₂]鈥?and a closer examination of these structures are provided. Also presented are the ¹⁷O NMR spectrum of an ¹⁷O-enriched sample of [PW₁₁O₃₉]^{7鈥?/sup> and a careful combined 31P NMR-titration study of the previously reported 鈥淜₇H₂[Au(O)(OH₂)P₂W₂₀O₇₀(OH₂)₂].鈥?These and considerable other data collectively indicate that previously assigned terminal Pt-oxo and Au-oxo complexes are in fact cocrystals of the all-tungsten structural analogues with noble metal cations, while the Pd-oxo complex is a disordered Pd(II)-substituted polyoxometalate. The neutron diffraction data have been re-analyzed, and new refinements are fully consistent with the all-tungsten formulations of the Pt-oxo and Au-oxo polyoxometalate species.}