J. Am. Chem. Soc., 127 (32), 11242 -11243, 2005. 10.1021/ja053497r S0002-7863(05)03497-9
Web Release Date: July 26, 2005

Copyright © 2005 American Chemical Society

Carbon Dioxide Reduction and Carbon Monoxide Activation Employing a Reactive Uranium(III) Complex

Ingrid Castro-Rodriguez and Karsten Meyer*

Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, MC 0358 La Jolla, California 92093-0358

kmeyer@ucsd.edu

Received May 28, 2005

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) -oxygen bridged complex [{((t-BuArO)3tacn)U}2(-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(-CO)] (4) with a CO ligand bridging two uranium ions in an unprecedented :1,1 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.

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