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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| Institution: | 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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