Publication Date:
2004-09-18
Description:
The electron-rich, six-coordinate tris-aryloxide uranium(III) complex [((AdArO)3tacn)U(III)] [where (AdArOH)3tacn = 1,4,7-tris(3-adamantyl-5-tert-butyl-2-hydroxybenzyl)1,4,7-triazacyclononane] reacts rapidly with CO2 to yield [((AdArO)3tacn)U(IV)(CO2)], a complex in which the CO(2) ligand is linearly coordinated to the metal through its oxygen atom (eta1-OCO). The latter complex has been crystallographically and spectroscopically characterized. The inequivalent O-C-O bond lengths [1.122 angstroms (A) for the O-C bond adjacent to uranium and 1.277 A for the other], considered together with magnetization data and electronic and vibrational spectra, support the following bonding model: U(IV)=O=C*-O- 〈--〉 U(IV)-OC-O-. In these charge-separated resonance structures, the uranium center is oxidized to uranium(IV) and the CO2 ligand reduced by one electron.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Castro-Rodriguez, Ingrid -- Nakai, Hidetaka -- Zakharov, Lev N -- Rheingold, Arnold L -- Meyer, Karsten -- 3 T32 DK07233-2651/DK/NIDDK NIH HHS/ -- New York, N.Y. -- Science. 2004 Sep 17;305(5691):1757-9.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, MC 0358, La Jolla, CA 92093, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15375263" target="_blank"〉PubMed〈/a〉
Keywords:
Carbon Dioxide/*chemistry
;
Crystallography
;
Electrons
;
Hydrophobic and Hydrophilic Interactions
;
Ligands
;
Magnetics
;
Models, Molecular
;
Molecular Structure
;
Oxidation-Reduction
;
Oxygen/*chemistry
;
Spectrum Analysis
;
Temperature
;
Uranium/*chemistry
;
X-Rays
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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