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

被引：89

作者：

Cleaves, Peter A. ^{[1
]}

King, David M. ^{[1
]}

Kefalidis, Christos E. ^{[2
,3
]}

Maron, Laurent ^{[2
,3
]}

Tuna, Floriana ^{[4
,5
]}

McInnes, Eric J. L. ^{[4
,5
]}

McMaster, Jonathan ^{[1
]}

Lewis, William ^{[1
]}

Blake, Alexander J. ^{[1
]}

Liddle, Stephen T. ^{[1
]}

机构：

[1] Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England

[2] Univ Toulouse 3, LPCNO, CNRS, F-31077 Toulouse, France

[3] Univ Toulouse 3, INSA, F-31077 Toulouse, France

[4] Univ Manchester, Sch Chem, Manchester M13 9PL, Lancs, England

[5] Univ Manchester, Photon Sci Inst, Manchester M13 9PL, Lancs, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 39期

基金：

英国工程与自然科学研究理事会;

关键词：

carbon monoxide; carbonylation; cyanates; nitrides; uranium; NITROGEN MULTIPLE BOND; INFRARED-SPECTRA; URANYL-ION; TRIPLE BOND; COMPLEXES; CO; COORDINATION; CHEMISTRY; LIGAND; ANALOG;

D O I：

10.1002/anie.201406203

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：10412 / 10415

页数：4

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