Carbon Dioxide Reduction and Carbon Monoxide Activation Employing a Reactive Uranium(III) Complex
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- 26 July 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (32) , 11242-11243
- https://doi.org/10.1021/ja053497r
Abstract
The highly reactive, six-coordinate tris-aryloxide U(III) species, [((t-BuArO)3tacn)U] (1) reacts with CO2 in a 2e- reduction to produce CO and a dinuclear U(IV/IV) μ-oxygen bridged complex [{((t-BuArO)3tacn)U}2(μ-O)] (2). This reaction proceeds via a dinuclear CO2-bridged intermediate 3. Also, mononuclear 1 was treated with 1 atm of CO to yield dinuclear [{((t-BuArO)3tacn)U}2(μ-CO)] (4) with a CO ligand bridging two uranium ions in an unprecedented μ:η 1,η1 fashion. The mixed-valent azido-bridged U(III/IV) complex 5 was synthesized from trivalent 1 and tetravalent [((t-BuArO)3tacn)U(N3)] and serves as an isostructural analogue of triatomic-bridged intermediate 3 as well as an electronic model for mixed-valent 4.Keywords
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