%0 Journal Article %A Castro-Rodriguez, Ingrid %A Meyer, Karsten %D 2005 %T Carbon Dioxide Reduction and Carbon Monoxide Activation Employing a Reactive Uranium(III) Complex %U https://acs.figshare.com/articles/journal_contribution/Carbon_Dioxide_Reduction_and_Carbon_Monoxide_Activation_Employing_a_Reactive_Uranium_III_Complex/3272842 %R 10.1021/ja053497r.s004 %2 https://ndownloader.figshare.com/files/5110558 %K isostructural analogue %K 2 e %K CO ligand %K 1 atm %K reaction proceeds %K uranium ions %K dinuclear CO 2 %K Carbon Monoxide Activation Employing %K trivalent 1 %K ArO %K CO 2 %K tacn %K carbon Dioxide Reduction %X 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,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. %I ACS Publications