Yes / 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.
| Identifer | oai:union.ndltd.org:BRADFORD/oai:bradscholars.brad.ac.uk:10454/9499 |
| Date | 23 March 2015 |
| Creators | 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. |
| Source Sets | Bradford Scholars |
| Language | English |
| Detected Language | English |
| Type | Article, Accepted manuscript |
| Rights | Unspecified |
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