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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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Version 2 2023-06-12, 06:38
Version 1 2023-06-09, 00:51
journal contribution
posted on 2023-06-12, 06:38 authored by Nikolaos Tsoureas, Alexander Kilpatrick, Christopher Inman, Geoff Cloke
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.

Funding

Reductive Transformations of Carbon Oxides RTCO; G0187; EUROPEAN UNION; 247390

Activation and Functionalisation of Carbon Dioxide by Low Valent Uranium Complexes; G1619; EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCIL; EP/M023885/1

History

Publication status

  • Published

File Version

  • Published version

Journal

Chemical Science

ISSN

2041-6539

Publisher

Royal Society of Chemistry

Issue

7

Volume

7

Page range

4624-4632

Department affiliated with

  • Chemistry Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2016-04-11

First Open Access (FOA) Date

2016-04-11

First Compliant Deposit (FCD) Date

2016-04-11

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