Synthesis of Electron-Rich Uranium (IV) Complexes Supported by Tridentate Schiff Base Ligands and Their Multi-Electron Redox Chemistry - Archive ouverte HAL
Article Dans Une Revue Inorganic Chemistry Année : 2013

Synthesis of Electron-Rich Uranium (IV) Complexes Supported by Tridentate Schiff Base Ligands and Their Multi-Electron Redox Chemistry

Résumé

he synthesis, structure, and reactivity of a new complex of U(IV) with the tridentate Schiff base ligand Menaphtquinolen are reported. The reduction of the bis-ligand complexes [UX2(Menaphtquinolen)2] (X = Cl, (1-Cl) ; I (1-I)) with potassium metal affords the U(IV) complex of the new tetranionic hexadentate ligand μ-bis-Menaphtquinolen formed through the intramolecular reductive coupling of the imino groups of each Menaphtquinolen unit. The solid state structure of the [U(μ-bis-Menaphtquinolen)]2 dimer 2 isolated from toluene confirms the presence of a U(IV) complex of the reduced ligand. Reactivity studies with molecular oxygen and 9,10-phenanthrenequinone show that complex 2 can act as a multielectron reducing agent releasing two electrons through the cleavage of the C–C bond to restore the original imino function of the ligand. In the resulting U(IV) and U(VI) complexes [U(9,10-phenanthrenediol)(Menaphtquinolen)2], 3, and [UO2(Menaphtquinolen)2], 4, the restored tridentate Schiff base allows for the coordination of the reduced substrate to the metal. Electrochemical studies of complex 2 show the presence of irreversible ligand centered reduction processes and of a reversible U(IV)/U(III) couple.

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hal-01877483 , version 1 (19-09-2018)

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Clément Camp, Julie Andrez, Jacques Pécaut, Marinella Mazzanti. Synthesis of Electron-Rich Uranium (IV) Complexes Supported by Tridentate Schiff Base Ligands and Their Multi-Electron Redox Chemistry. Inorganic Chemistry, 2013, 52 (12), pp.7078--7086. ⟨10.1021/ic4006218⟩. ⟨hal-01877483⟩
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