Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex

被引：85

作者：

Lu, Erli ^{[1
]}

Cooper, Oliver J. ^{[1
]}

McMaster, Jonathan ^{[1
]}

Tuna, Floriana ^{[2
,3
]}

McInnes, Eric J. L. ^{[2
,3
]}

Lewis, William ^{[1
]}

Blake, Alexander J. ^{[1
]}

Liddle, Stephen T. ^{[1
]}

机构：

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

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

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

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 26期

基金：

欧洲研究理事会; 英国工程与自然科学研究理事会;

关键词：

carbene ligands; imido ligands; multiple bonding; oxo ligands; uranium; VALENT ORGANOURANIUM COMPLEXES; ONE-ELECTRON OXIDATION; CARBON MULTIPLE-BOND; MOLECULAR-STRUCTURE; URANYL(VI) ION; FACILE ACCESS; U-IV=C; LIGAND; CHEMISTRY; ANALOGS;

D O I：

10.1002/anie.201403892

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report the uranium(VI) carbene imido oxo complex [U(BIPMTMS)(NMes)(O)(DMAP)(2)] (5, BIPMTMS = C(PPh2NSiMe3)(2); Mes=2,4,6-Me3C6H2; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPMTMS)(O)(2)(DMAP)(2)] (6).

引用

页码：6696 / 6700

页数：5

共 78 条

[1]

[Anonymous], 2013, ANGEW CHEM INT EDIT

[2] SYNTHESIS AND PROPERTIES OF HIGH-VALENT ORGANOURANIUM COMPLEXES CONTAINING TERMINAL ORGANOIMIDO AND OXO FUNCTIONAL-GROUPS - A NEW CLASS OF ORGANO-F-ELEMENT COMPLEXES [J].