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Issue 1, 2017
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Inner-sphere vs. outer-sphere reduction of uranyl supported by a redox-active, donor-expanded dipyrrin

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Abstract

The uranyl(VI) complex UO2Cl(L) of the redox-active, acyclic diimino-dipyrrin anion, L is reported and its reaction with inner- and outer-sphere reductants studied. Voltammetric, EPR-spectroscopic and X-ray crystallographic studies show that chemical reduction by the outer-sphere reagent CoCp2 initially reduces the ligand to a dipyrrin radical, and imply that a second equivalent of CoCp2 reduces the U(VI) centre to form U(V). Cyclic voltammetry indicates that further outer-sphere reduction to form the putative U(IV) trianion only occurs at strongly cathodic potentials. The initial reduction of the dipyrrin ligand is supported by emission spectra, X-ray crystallography, and DFT; the latter also shows that these outer-sphere reactions are exergonic and proceed through sequential, one-electron steps. Reduction by the inner-sphere reductant [TiCp2Cl]2 is also likely to result in ligand reduction in the first instance but, in contrast to the outer-sphere case, reduction of the uranium centre becomes much more favoured, allowing the formation of a crystallographically characterised, doubly-titanated U(IV) complex. In the case of inner-sphere reduction only, ligand-to-metal electron-transfer is thermodynamically driven by coordination of Lewis-acidic Ti(IV) to the uranyl oxo, and is energetically preferable over the disproportionation of U(V). Overall, the involvement of the redox-active dipyrrin ligand in the reduction chemistry of UO2Cl(L) is inherent to both inner- and outer-sphere reduction mechanisms, providing a new route to accessing a variety of U(VI), U(V), and U(IV) complexes.

Graphical abstract: Inner-sphere vs. outer-sphere reduction of uranyl supported by a redox-active, donor-expanded dipyrrin

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Publication details

The article was received on 01 Jul 2016, accepted on 11 Oct 2016 and first published on 28 Oct 2016


Article type: Edge Article
DOI: 10.1039/C6SC02912D
Chem. Sci., 2017,8, 108-116
  • Open access: Creative Commons BY license
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    Inner-sphere vs. outer-sphere reduction of uranyl supported by a redox-active, donor-expanded dipyrrin

    J. R. Pankhurst, N. L. Bell, M. Zegke, L. N. Platts, C. A. Lamfsus, L. Maron, L. S. Natrajan, S. Sproules, P. L. Arnold and J. B. Love, Chem. Sci., 2017, 8, 108
    DOI: 10.1039/C6SC02912D

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