A Trivalent Bis(acyl)phosphide Complex of Uranium

A Trivalent Bis(acyl)phosphide Complex of Uranium

Author: European Journal of Inorganic Chemistry

Bis(acyl)phosphides (BAPs) such as bis(mesitoyl)phosphide (mesBAP) are phosphorus analogs of acetylacetonate (acac) derivatives. These compounds can be used in f-element coordination chemistry as chelating ligands. So far, bis(acyl)phosphide complexes of uranium had been limited to tetravalent uranium, as in [UIV(mesBAP)4].

Karsten Meyer, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen, Germany, and colleagues have isolated the complex salts K[UIII(mesBAP)4] (pictured) and K(2.2.2-cryptand)][UIII(mesBAP)4]. The compounds feature a genuine trivalent uranium complex with four bidentate chelating mesBAP ligands. The complex was obtained by the reduction of its tetravalent analogue [UIV(mesBAP)4] using KC8 in tetrahydrofuran (THF) at room temperature. The products were characterized spectroscopically, electrochemically, and magnetochemically to confirm the uranium ion’s +III oxidation state.

Overall, the work introduces a new ligand to low-valent uranium coordination chemistry. It allows for the synthesis of an isostructural UIII/UIV redox pair and could be promising for small-molecule activation chemistry.



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