Journal Article

PreJuSER-22351

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Revisiting the Polyoxometalate-Based Late-Transition-Metal-Oxo Complexes: The "Oxo Wall" Stands

OHalloran, K. P. ; Zhao, C. ; Ando, N. S. ; Schultz, A. J. ; Koetzle, T. F. ; Piccoli, P. M. B. ; Hedman, B. ; Hodgson, K. O. ; Bobyr, E. ; Kirk, M. L. ; Knottenbelt, S. ; Depperman, E. C. ; Stein, B. ; Anderson, T. M. ; Cao, R. ; Geletii, Y. V. ; Hardcastle, K. I. ; Musaev, D. G. ; Neiwert, W. A. ; Fang, X. ; Morokuma, K. ; Wu, S.FZJ* ; Kögerler, P.FZJ* ; Hill, C. L.

2012
American Chemical Society Washington, DC

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Please use a persistent id in citations: doi:10.1021/ic2008914

Abstract: 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 (17)O and (31)P 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 K(14)[P(2)W(19)O(69)(OH(2))] and "K(10)Na(3)[Pd(IV)(O)(OH)WO(OH(2))(PW(9)O(34))(2)]" and a closer examination of these structures are provided. Also presented are the (17)O NMR spectrum of an (17)O-enriched sample of [PW(11)O(39)](7-) and a careful combined (31)P NMR-titration study of the previously reported "K(7)H(2)[Au(O)(OH(2))P(2)W(20)O(70)(OH(2))(2)]." 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.

Keyword(s): J

Note: We thank the National Science Foundation (grant CHE-0911610) for support of this research. We also thank Dr. Ulrich Kortz of Jacobs University (Bremen, Germany) for challenging our work.

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Contributing Institute(s):

1. Elektronische Eigenschaften (PGI-6)

Research Program(s):

1. Grundlagen für zukünftige Informationstechnologien (P42)

Appears in the scientific report 2012

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Database coverage:
; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection ; Zoological Record

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