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.

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.

Citation

Cleaves, P. A., King, D. M., Kefalidis, C. E., Maron, L., Tuna, F., McInnes, E. J., McMaster, J., Lewis, W., Blake, A. 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

• Journal Article Type: Article
• Acceptance Date: Jul 30, 2014
• Online Publication Date: Jul 30, 2014
• Publication Date: Sep 22, 2014
• Deposit Date: Sep 28, 2017
• Publicly Available Date: Sep 28, 2017
• 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
• DOI: https://doi.org/10.1002/anie.201406203
• Keywords: carbon monoxide; carbonylation; cyanates; nitrides; uranium
• Public URL: https://nottingham-repository.worktribe.com/output/735742
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/anie.201406203/abstract
• Contract Date: Sep 28, 2017