A Late-Transition Metal Oxo Complex: K 7 Na 9 [O=Pt IV (H 2 O)L 2 ], L = [PW 9 O 34 ] 9--Reference-Cited by-同舟云学术

A Late-Transition Metal Oxo Complex: K 7 Na 9 [O=Pt IV (H 2 O)L 2 ], L = [PW 9 O 34 ] 9-

Published:2004-12-17 Issue:5704 Volume:306 Page:2074-2077
ISSN:0036-8075
Container-title:Science
language:en
Short-container-title:Science

Author:

Anderson Travis M.¹²³,Neiwert Wade A.¹²³,Kirk Martin L.¹²³,Piccoli Paula M. B.¹²³,Schultz Arthur J.¹²³,Koetzle Thomas F.¹²³,Musaev Djamaladdin G.¹²³,Morokuma Keiji¹²³,Cao Rui¹²³,Hill Craig L.¹²³

Affiliation:

1. Department of Chemistry, Emory University, Atlanta, GA 30322, USA.

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.

Abstract

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 7 Na 9 [O=Pt(H 2 O)L 2 ], L = [PW 9 O 34 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.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

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