Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 39, Pages 10412-10415Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201406203
Keywords
carbon monoxide; carbonylation; cyanates; nitrides; uranium
Categories
Funding
- Royal Society
- EPSRC
- ERC
- University of Nottingham
- COST Action [CM1006]
- National Nuclear Laboratory
- Humboldt foundation
- EPSRC [EP/G051763/1, EP/K024000/1, EP/K038869/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K024000/1, EP/G051763/1, EP/K038869/1] Funding Source: researchfish
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Two-electron reductive carbonylation of the uranium(VI) nitride [U(Tren(TIPS))(N)] (2, Tren(TIPS) = N(CH(2)CH(2)NSiiPr(3))(3)) with CO gave the uranium(IV) cyanate [U(Tren(TIPS))(NCO)] (3). KC8 reduction of 3 resulted in cyanate dissociation to give [U(Tren(TIPS))] (4) and KNCO, or cyanate retention in [U(Tren(TIPS))(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(Tren(TIPS))(N)K}(2)] (6), with or without B15C5, respectively. Complex 5 can be prepared directly from CO and [U(Tren(TIPS))(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 pi* orbital of CO by the nitride with activation energy barriers of 24.7 and 11.3 kcalmol(-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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