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@ARTICLE{OHalloran:22351,
author = {OHalloran, K.P. and Zhao, C. and Ando, N.S. and Schultz,
A.J. and Koetzle, T.F. and Piccoli, P.M.B. and Hedman, B.
and Hodgson, K.O. and Bobyr, E. and Kirk, M.L. and
Knottenbelt, S. and Depperman, E.C. and Stein, B. and
Anderson, T.M. and Cao, R. and Geletii, Y.V. and Hardcastle,
K.I. and Musaev, D.G. and Neiwert, W.A. and Fang, X. and
Morokuma, K. and Wu, S. and Kögerler, P. and Hill, C.L.},
title = {{R}evisiting the {P}olyoxometalate-{B}ased
{L}ate-{T}ransition-{M}etal-{O}xo {C}omplexes: {T}he "{O}xo
{W}all" {S}tands},
journal = {Inorganic chemistry},
volume = {51},
issn = {0020-1669},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PreJuSER-22351},
pages = {7025 - 7031},
year = {2012},
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.},
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.},
keywords = {J (WoSType)},
cin = {PGI-6},
ddc = {540},
cid = {I:(DE-Juel1)PGI-6-20110106},
pnm = {Grundlagen für zukünftige Informationstechnologien},
pid = {G:(DE-Juel1)FUEK412},
shelfmark = {Chemistry, Inorganic $\&$ Nuclear},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:22694272},
UT = {WOS:000305853600009},
doi = {10.1021/ic2008914},
url = {https://juser.fz-juelich.de/record/22351},
}