Two-Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Angewandte Chemie International Edition Year : 2014

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

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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Dates and versions

hal-01969445 , version 1 (04-01-2019)

Identifiers

  • HAL Id : hal-01969445 , version 1

Cite

Peter Cleaves, David King, Christos E. Kefalidis, Laurent Maron, Floriana Tuna, et al.. Two-Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide. Angewandte Chemie International Edition, 2014, 53 (39), pp.10412-10415. ⟨hal-01969445⟩
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