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Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions

Cleaves, Peter A.; Kefalidis, Christos E.; Gardner, Benedict M.; Tuna, Floriana; McInnes, Eric J.L.; Lewis, William; Maron, Laurent; Liddle, Stephen T.

Authors

Peter A. Cleaves

Christos E. Kefalidis

Benedict M. Gardner

Floriana Tuna

Eric J.L. McInnes

William Lewis

Laurent Maron

Stephen T. Liddle



Abstract

The reactivity of terminal uranium(V/VI) nitrides with CE2 (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(TrenTIPS)(N)][K(B15C5)2] (1, TrenTIPS=N(CH2CH2NSiiPr3)3; B15C5=benzo-15-crown-5) reacts with CO2 to give [U(TrenTIPS)(O)(NCO)][K(B15C5)2] (3), whereas the uranium(VI) nitride [U(TrenTIPS)(N)] (2) reacts with CO2 to give isolable [U(TrenTIPS)(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(TrenTIPS)(O)] (5) with concomitant formation of N2 and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS2 to give [U(TrenTIPS)(κ2-CS3)][K(B15C5)2] (6), 2, and [K(B15C5)2][NCS] (7), whereas 2 reacts with CS2 to give [U(TrenTIPS)(NCS)] (8) and “S”, with the latter trapped as Ph3PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE2 follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS2 as a reactivity surrogate for CO2.

Journal Article Type Article
Publication Date Feb 24, 2017
Journal Chemistry - a European Journal
Print ISSN 0947-6539
Electronic ISSN 1521-3765
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 23
Issue 12
APA6 Citation Cleaves, P. A., Kefalidis, C. E., Gardner, B. M., Tuna, F., McInnes, E. J., Lewis, W., …Liddle, S. T. (2017). Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide: factors governing diverse and well-defined cleavage and redox reactions. Chemistry - A European Journal, 23(12), doi:10.1002/chem.201605620
DOI https://doi.org/10.1002/chem.201605620
Keywords carbon dioxide; carbon disulfide; density functional theory; nitride; uranium
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/chem.201605620/abstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
Additional Information This is the peer reviewed version of the following article: P. A. Cleaves, C. E. Kefalidis, B. M. Gardner, F. Tuna, E. J. L. McInnes, W. Lewis, L. Maron, S. T. Liddle, Chem. Eur. J. 2017, 23, 2950, which has been published in final form at http://dx.doi.org/10.1002/chem.201605620. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf





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