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

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 exergoni

SUBMITTER: Pankhurst JR 

PROVIDER: S-EPMC5304617 | biostudies-literature | 2017 Jan

REPOSITORIES: biostudies-literature