Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U(v) oxo and nitrido complexes

Chemical Science
Nikolaos TsoureasF Geoffrey N Cloke

Abstract

The synthesis and molecular structures of a U(v) neutral terminal oxo complex and a U(v) sodium uranium nitride contact ion pair are described. The synthesis of the former is achieved by the use of t BuNCO as a mild oxygen transfer reagent, whilst that of the latter is via the reduction of NaN3. Both mono-uranium complexes are stabilised by the presence of bulky silyl substituents on the ligand framework that facilitate a 2e- oxidation of a single U(iii) centre. In contrast, when steric hindrance around the metal centre is reduced by the use of less bulky silyl groups, the products are di-uranium, U(iv) bridging oxo and (anionic) nitride complexes, resulting from 1e- oxidations of two U(iii) centres. SQUID magnetometry supports the formal oxidation states of the reported complexes. Electrochemical studies show that the U(v) terminal oxo complex can be reduced and the [U(iv)O]- anion was accessed via reduction with K/Hg, and structurally characterised. Both the nitride complexes display complex electrochemical behaviour but each exhibits a quasi-reversible oxidation at ca. -1.6 V vs. Fc+/0.

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Citations

Mar 15, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Aurélien R WillauerMarinella Mazzanti
Apr 30, 2019·Angewandte Chemie·Fu-Sheng GuoRichard A Layfield
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Dec 21, 2019·Journal of the American Chemical Society·Nikolaos TsoureasF Geoffrey N Cloke
Jan 16, 2020·Journal of the American Chemical Society·Chad T PalumboMarinella Mazzanti
Aug 18, 2021·Chemistry : a European Journal·Michael L TarltonJustin R Walensky

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Methods Mentioned

BETA
X-ray
NMR
cyclic voltammetry

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