A Late-Transition Metal Oxo Complex: K7Na9[O=PtIV(H2O)L2], L = [PW9O34]9-
Travis M. Anderson,1
Wade A. Neiwert,1*
Martin L. Kirk,2
Paula M. B. Piccoli,3
Arthur J. Schultz,3
Thomas F. Koetzle,3
Djamaladdin G. Musaev,1
Keiji Morokuma,1
Rui Cao,1
Craig L. Hill1
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, K
7Na
9[O=Pt(H
2O)L
2], L = [PW
9O
349–],
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.
2 Department of Chemistry, The University of New Mexico, Albuquerque, NM 87131–0001, USA.
3 Intense Pulsed Neutron Source, Argonne National Laboratory, Argonne, IL 60439, USA.
* Present address: Department of Chemistry, Bethel University, St. Paul, MN 55112, USA.
To whom correspondence should be addressed. E-mail: chill{at}emory.edu
