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Communication

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

Supporting Info

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

J. Am. Chem. Soc., 2005, 127 (32), pp 11242–11243

DOI: 10.1021/ja053497r

Publication Date (Web): July 26, 2005

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, kmeyer@ucsd.edu

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:η¹,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.

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Published In Issue August 17, 2005
Received May 28, 2005

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Communication

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