Control of Oxo-Group Functionalization and Reduction of the Uranyl Ion
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2015-04Author
Arnold, P.L.Pécharman, A-F.
Lord, Rianne M.
Jones, G.M.
Hollis, E.
Nichol, G.S.
Maron, L.
Fang, J.
Davin, T.
Love, J.B.
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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-oxogroup.Version
Accepted manuscriptCitation
Arnold PL, Pécharman AF, Lord RM, Jones GM, Hollis E, Nichol GS, Maron L, Fang J, Davin T and Love JB (2015) Control of Oxo-Group Functionalization and Reduction of the Uranyl Ion. Inorganic Chemistry. 54 (7): 3702−3710.Link to Version of Record
https://doi.org/10.1021/acs.inorgchem.5b00420Type
Articleae974a485f413a2113503eed53cd6c53
https://doi.org/10.1021/acs.inorgchem.5b00420