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dc.contributor.authorArnold, P.L.*
dc.contributor.authorPécharman, A-F.*
dc.contributor.authorLord, Rianne M.*
dc.contributor.authorJones, G.M.*
dc.contributor.authorHollis, E.*
dc.contributor.authorNichol, G.S.*
dc.contributor.authorMaron, L.*
dc.contributor.authorFang, J.*
dc.contributor.authorDavin, T.*
dc.contributor.authorLove, J.B.*
dc.date.accessioned2016-09-30T11:30:09Z
dc.date.available2016-09-30T11:30:09Z
dc.date.issued2015-04
dc.identifier.citationArnold 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.en_US
dc.identifier.urihttp://hdl.handle.net/10454/9499
dc.descriptionyesen_US
dc.description.abstractUranyl 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.en_US
dc.language.isoenen_US
dc.relation.isreferencedbyhttp://dx.doi.org/10.1021/acs.inorgchem.5b00420en_US
dc.subjectOxo-Group functionalization; Uranyl Ion; Oxo-silylated uranyl Pacman complexesen_US
dc.titleControl of Oxo-Group Functionalization and Reduction of the Uranyl Ionen_US
dc.status.refereedyesen_US
dc.date.application2015-03-23
dc.typeArticleen_US
dc.type.versionAccepted manuscripten_US


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