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Issue 7, 2016
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Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U(v) oxo and nitrido complexes

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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 tBuNCO 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.

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

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Article information


Submitted
10 Feb 2016
Accepted
08 Apr 2016
First published
11 Apr 2016

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2016,7, 4624-4632
Article type
Edge Article
Author version available

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

N. Tsoureas, A. F. R. Kilpatrick, C. J. Inman and F. G. N. Cloke, Chem. Sci., 2016, 7, 4624
DOI: 10.1039/C6SC00632A

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