Skip to main content

Research Repository

Advanced Search

Two-Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide

Cleaves, Peter A.; King, David M.; Kefalidis, Christos E.; Maron, Laurent; Tuna, Floriana; McInnes, Eric J.L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

Authors

Peter A. Cleaves

David M. King

Christos E. Kefalidis

Laurent Maron

Floriana Tuna

Eric J.L. McInnes

William Lewis

Alexander J. Blake

Stephen T. Liddle



Abstract

Two-electron reductive carbonylation of the uranium(VI) nitride [U(TrenTIPS)(N)] (2, TrenTIPS=N(CH2CH2NSiiPr3)3) with CO gave the uranium(IV) cyanate [U(TrenTIPS)(NCO)] (3). KC8 reduction of 3 resulted in cyanate dissociation to give [U(TrenTIPS)] (4) and KNCO, or cyanate retention in [U(TrenTIPS)(NCO)][K(B15C5)2] (5, B15C5=benzo-15-crown-5 ether) with B15C5. Complexes 5 and 4 and KNCO were also prepared from CO and the uranium(V) nitride [{U(TrenTIPS)(N)K}2] (6), with or without B15C5, respectively. Complex 5 can be prepared directly from CO and [U(TrenTIPS)(N)][K(B15C5)2] (7). Notably, 7 reacts with CO much faster than 2. This unprecedented f-block reactivity was modeled theoretically, revealing nucleophilic attack of the π* orbital of CO by the nitride with activation energy barriers of 24.7 and 11.3 kcal mol−1 for uranium(VI) and uranium(V), respectively. A remarkably simple two-step, two-electron cycle for the conversion of azide to nitride to cyanate using 4, NaN3 and CO is presented.

Journal Article Type Article
Publication Date Sep 22, 2014
Journal Angewandte Chemie International Edition
Print ISSN 1433-7851
Electronic ISSN 1521-3773
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 53
Issue 39
Pages 10412-10415
APA6 Citation Cleaves, P. A., King, D. M., Kefalidis, C. E., Maron, L., Tuna, F., McInnes, E. J., …Liddle, S. T. (2014). Two-Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide. Angewandte Chemie International Edition, 53(39), 10412-10415. https://doi.org/10.1002/anie.201406203
DOI https://doi.org/10.1002/anie.201406203
Keywords carbon monoxide; carbonylation; cyanates; nitrides; uranium
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/anie.201406203/abstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0

Files

Cleaves_et_al-2014-Angewandte_Chemie_International_Edition.pdf (845 Kb)
PDF

Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0





You might also like



Downloadable Citations

;