Article Dans Une Revue Angewandte Chemie International Edition Année : 2023

A Route to Stabilize Uranium(II) and Uranium(I) Synthons in Multimetallic Complexes

Résumé

Herein, we report the redox reactivity of a multimetallic uranium complex supported by triphenylsiloxide (−OSiPh 3 ) ligands, where we show that low valent synthons can be stabilized via an unprecedented mechanism involving intramolecular ligand migration. The two‐ and three‐electron reduction of the oxo‐bridged diuranium(IV) complex [{(Ph 3 SiO) 3 (DME)U} 2 ( μ ‐O)], 4 , yields the formal “U II /U IV ”, 5 , and “U I /U IV ”, 6 , complexes via ligand migration and formation of uranium‐arene δ‐bond interactions. Remarkably, complex 5 effects the two‐electron reductive coupling of pyridine affording complex 7 , which demonstrates that the electron‐transfer is accompanied by ligand migration, restoring the original ligand arrangement found in 4 . This work provides a new method for controlling the redox reactivity in molecular complexes of unstable, low‐valent metal centers, and can lead to the further development of f ‐elements redox reactivity.

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Dates et versions

hal-04281546 , version 1 (13-11-2023)

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R. Keerthi Shivaraam, Megan Keener, Dieuwertje Modder, Thayalan Rajeshkumar, Ivica Živković, et al.. A Route to Stabilize Uranium(II) and Uranium(I) Synthons in Multimetallic Complexes. Angewandte Chemie International Edition, 2023, 62 (23), pp.e202304051. ⟨10.1002/anie.202304051⟩. ⟨hal-04281546⟩
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