Two‐Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide |
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| Authors: | Peter A. Cleaves Dr. David M. King Dr. Christos E. Kefalidis Prof. Laurent Maron Dr. Floriana Tuna Prof. Eric J. L. McInnes Dr. Jonathan McMaster Dr. William Lewis Prof. Alexander J. Blake Prof. Stephen T. Liddle |
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| Affiliation: | 1. School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK);2. LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077 Toulouse (France);3. School of Chemistry and Photon Science Institute, University of Manchester, Oxford Road, Manchester, M13 9PL (UK) |
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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. |
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| Keywords: | carbon monoxide carbonylation cyanates nitrides uranium |
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