TY - DATA T1 - Carbon Dioxide Reduction and Carbon Monoxide Activation Employing a Reactive Uranium(III) Complex PY - 2005/08/17 AU - Ingrid Castro-Rodriguez AU - Karsten Meyer UR - https://acs.figshare.com/articles/journal_contribution/Carbon_Dioxide_Reduction_and_Carbon_Monoxide_Activation_Employing_a_Reactive_Uranium_III_Complex/3272842 DO - 10.1021/ja053497r.s004 L4 - https://ndownloader.figshare.com/files/5110558 KW - isostructural analogue KW - 2 e KW - CO ligand KW - 1 atm KW - reaction proceeds KW - uranium ions KW - dinuclear CO 2 KW - Carbon Monoxide Activation Employing KW - trivalent 1 KW - ArO KW - CO 2 KW - tacn KW - carbon Dioxide Reduction N2 - 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. ER -