A Linear, O-Coordinated η 1 -CO 2 Bound to Uranium
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- 17 September 2004
- journal article
- other
- Published by American Association for the Advancement of Science (AAAS) in Science
- Vol. 305 (5691) , 1757-1759
- https://doi.org/10.1126/science.1102602
Abstract
The electron-rich, six-coordinate tris-aryloxide uranium(III) complex [((AdArO)3tacn)UIII] [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)UIV(CO2)], a complex in which the CO2 ligand is linearly coordinated to the metal through its oxygen atom (η1-OCO). The latter complex has been crystallographically and spectroscopically characterized. The inequivalent O–C–O bond lengths [1.122 angstroms (Å) for the O–C bond adjacent to uranium and 1.277 Å for the other], considered together with magnetization data and electronic and vibrational spectra, support the following bonding model: UIV=O=C⚫–O– ↔ UIV–O C–O–. In these charge-separated resonance structures, the uranium center is oxidized to uranium(IV) and the CO2 ligand reduced by one electron.Keywords
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