Two-electron reductive carbonylation of terminal uranium(V) and uranium(VI) nitrides to cyanate by carbon monoxide

Cleaves, Peter A. and King, David M. and Kefalidis, Christos E. and Maron, Laurent and Tuna, Floriana and McInnes, Eric J.L. and McMaster, Jonathan and Lewis, William and Blake, Alexander J. and Liddle, Stephen 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). pp. 10412-10415. ISSN 1521-3773

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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.

Item Type: Article
Keywords: carbon monoxide; carbonylation; cyanates; nitrides; uranium
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Chemistry
Identification Number: 10.1002/anie.201406203
Depositing User: Lewis, William
Date Deposited: 28 Sep 2017 11:20
Last Modified: 14 Oct 2017 08:23
URI: http://eprints.nottingham.ac.uk/id/eprint/46634

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