Control of Oxo-group functionalization and reduction of the uranyl ion

Arnold, Polly L., Pécharman, Anne-Frédérique, Lord, Rianne M., Jones, Guy M., Hollis, Emmalina, Nichol, Gary S., Maron, Laurent, Fang, Jian, Davin, Thomas and Love, Jason B. (2015) Control of Oxo-group functionalization and reduction of the uranyl ion. Inorganic Chemistry, 54 (7). pp. 3702-3710. ISSN 0020-1669

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Abstract

Uranyl complexes of a large, compartmental N8-macrocycle adopt a rigid, “Pacman” geometry that stabilizes the UV oxidation state and promotes chemistry at a single uranyl oxo-group. We present here new and straightforward routes to singly reduced and oxo-silylated uranyl Pacman complexes and propose mechanisms that account for the product formation, and the byproduct distributions that are formed using alternative reagents. Uranyl(VI) Pacman complexes in which one oxo-group is functionalized by a single metal cation are activated toward single-electron reduction. As such, the addition of a second equivalent of a Lewis acidic metal complex such as MgN″2 (N″ = N(SiMe3)2) forms a uranyl(V) complex in which both oxo-groups are Mg functionalized as a result of Mg–N bond homolysis. In contrast, reactions with the less Lewis acidic complex [Zn(N″)Cl] favor the formation of weaker U–O–Zn dative interactions, leading to reductive silylation of the uranyl oxo-group in preference to metalation. Spectroscopic, crystallographic, and computational analysis of these reactions and of oxo-metalated products isolated by other routes have allowed us to propose mechanisms that account for pathways to metalation or silylation of the exo-oxo-group.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 30 Jan 2020 04:15
Last Modified: 22 Apr 2020 08:35
URI: https://ueaeprints.uea.ac.uk/id/eprint/73876
DOI: 10.1021/acs.inorgchem.5b00420

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