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Arnold, Polly L., Pécharman, Anne-Frédérique, Lord, Rianne M. 
ORCID: https://orcid.org/0000-0001-9981-129X, 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
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 |
| UEA Research Groups: | Faculty of Science > Research Groups > Chemistry of Materials and Catalysis Faculty of Science > Research Groups > Chemistry of Life Processes Faculty of Science > Research Centres > Centre for Molecular and Structural Biochemistry |
| Related URLs: | |
| Depositing User: | LivePure Connector |
| Date Deposited: | 30 Jan 2020 04:15 |
| Last Modified: | 22 Oct 2022 05:46 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/73876 |
| DOI: | 10.1021/acs.inorgchem.5b00420 |
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