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

Tsoureas, Nikolaos, Kilpatrick, Alexander, Inman, Christopher and Cloke, Frederick Geoffrey (2016) Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U(V) oxo and nitrido complexes. Chemical Science, 7 (7). pp. 4624-4632. ISSN 2041-6539

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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.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0146 Inorganic chemistry
Depositing User: Geoff Cloke
Date Deposited: 11 Apr 2016 11:13
Last Modified: 12 Sep 2017 14:01
URI: http://sro.sussex.ac.uk/id/eprint/60407

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Project NameSussex Project NumberFunderFunder Ref
Activation and Functionalisation of Carbon Dioxide by Low Valent Uranium ComplexesG1619EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCILEP/M023885/1
Reductive Transformations of Carbon Oxides RTCOG0187EUROPEAN UNION247390