一氧化碳将末端铀（V）和铀（VI）氮化物双电子还原羰基化生成氰酸盐。
Two-electron reductive carbonylation of terminal uranium(V) and uranium(VI) nitrides to cyanate by carbon monoxide.
作者信息
Cleaves Peter A, King David M, Kefalidis Christos E, Maron Laurent, Tuna Floriana, McInnes Eric J L, McMaster Jonathan, Lewis William, Blake Alexander J, Liddle Stephen T
机构信息
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (UK).
出版信息
Angew Chem Int Ed Engl. 2014 Sep 22;53(39):10412-5. doi: 10.1002/anie.201406203. Epub 2014 Jul 30.
Two-electron reductive carbonylation of the uranium(VI) nitride [U(Tren(TIPS))(N)] (2, Tren(TIPS)=N(CH2CH2NSiiPr3)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 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.
铀（VI）氮化物[U(Tren(TIPS))(N)]（2，Tren(TIPS)=N(CH2CH2NSiiPr3)3）与CO发生双电子还原羰基化反应生成铀（IV）氰酸盐[U(Tren(TIPS))(NCO)]（3）。3经KC8还原导致氰酸根解离生成[U(Tren(TIPS))]（4）和KNCO，或者在[U(Tren(TIPS))(NCO)][K(B15C5)2]（5，B15C5=苯并-15-冠-5醚）中氰酸根与B15C5结合保留。配合物5和4以及KNCO也分别由CO与铀（V）氮化物[{U(Tren(TIPS))(N)K}2]（6）制备，反应中分别添加或不添加B15C5。配合物5可直接由CO与[U(Tren(TIPS))(N)][K(B15C5)2]（7）制备。值得注意的是，7与CO的反应比2快得多。对这种前所未有的f族元素反应活性进行了理论模拟，结果表明氮化物对CO的π*轨道进行亲核进攻，铀（VI）和铀（V）的活化能垒分别为24.7和11.3 kcal mol(-1)。本文提出了一个使用4、NaN3和CO将叠氮化物转化为氮化物再转化为氰酸盐的极为简单的两步双电子循环。
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