Publication Date:
2004-11-27
Description:
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, K7Na9[O=Pt(H2O)L2], L = [PW9O34(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.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Anderson, Travis M -- Neiwert, Wade A -- Kirk, Martin L -- Piccoli, Paula M B -- Schultz, Arthur J -- Koetzle, Thomas F -- Musaev, Djamaladdin G -- Morokuma, Keiji -- Cao, Rui -- Hill, Craig L -- GM-057378/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 2004 Dec 17;306(5704):2074-7. Epub 2004 Nov 25.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Emory University, Atlanta, GA 30322, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15564312" target="_blank"〉PubMed〈/a〉
Keywords:
Chemistry, Physical
;
Crystallization
;
Crystallography, X-Ray
;
Electrons
;
Fourier Analysis
;
Hydrogen-Ion Concentration
;
Ligands
;
Molecular Structure
;
Neutron Diffraction
;
Oxidation-Reduction
;
Oxygen/*chemistry
;
Physicochemical Phenomena
;
Platinum/chemistry
;
Platinum Compounds/chemical synthesis/*chemistry/isolation & purification
;
Spectrum Analysis
;
Temperature
;
Tungsten/chemistry
;
Tungsten Compounds/chemical synthesis/*chemistry/isolation & purification
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
,
Chemistry and Pharmacology
,
Computer Science
,
Medicine
,
Natural Sciences in General
,
Physics
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