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Synthesis and Reduction of Uranium(V) Imido Complexes with Redox‐Active Substituents
15
Citations
76
References
2017
Year
Organic azides that contain naphthyl functional groups were used to prepare uranium(V) imido complexes U<sup>V</sup> [=NC(2-naph)Ph<sub>2</sub> ][N(SiMe<sub>3</sub> )<sub>2</sub> ]<sub>3</sub> (2), U<sup>V</sup> [=NC(2-naph)<sub>3</sub> ][N(SiMe<sub>3</sub> )<sub>2</sub> ]<sub>3</sub> (3), and U<sup>V</sup> [=N(2-naph)][N(SiMe<sub>3</sub> )<sub>2</sub> ]<sub>3</sub> (4), and their properties were compared with U<sup>V</sup> [=NCPh<sub>3</sub> ][N(SiMe<sub>3</sub> )<sub>2</sub> ]<sub>3</sub> (1). The electronic structures of these compounds were investigated by solution electrochemistry studies, which revealed accessible U<sup>V/VI</sup> , U<sup>IV/V</sup> , and naphthalene<sup>0</sup> /naphthalene<sup>-1</sup> couples. The uranium(V) naphthylimido complexes were reduced by potassium graphite to yield their uranium(IV) congeners K[U<sup>IV</sup> [=NC(2-naph)Ph<sub>2</sub> ][N(SiMe<sub>3</sub> )<sub>2</sub> ]<sub>3</sub> ] (2-K), K[U<sup>IV</sup> [=NC(2-naph)<sub>3</sub> ][N(SiMe<sub>3</sub> )<sub>2</sub> ]<sub>3</sub> ] (3-K), and K[U<sup>IV</sup> [=N(2-naph)][N(SiMe<sub>3</sub> )<sub>2</sub> ]<sub>3</sub> ] (4-K). The electronic structure of the dianionic compounds were investigated by DFT calculations, and this revealed that the second reduction was ligand-based, which opens the possibility of accomplishing multi-electron redox chemistry by using a tailored multiply-bonded ligand.
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