Normal-to-Abnormal Rearrangement and NHC Activation in Three-Coordinate Iron(II) Carbene Complexes

被引：106

作者：

Day, Benjamin M. ^{[1
]}

Pugh, Thomas ^{[1
]}

Hendriks, Daniel ^{[3
]}

Guerra, Celia Fonseca ^{[3
]}

Evans, David J. ^{[2
]}

Bickelhaupt, F. Matthias ^{[3
,4
]}

Layfield, Richard A. ^{[1
]}

机构：

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

[2] Univ Hull, Dept Chem, Kingston Upon Hull HU6 7RX, N Humberside, England

[3] Vrije Univ Amsterdam, Dept Theoret Chem, Amsterdam Ctr Multiscale Modeling, NL-1081 HV Amsterdam, Netherlands

[4] Radboud Univ Nijmegen, Inst Mol & Mat, NL-6525 AJ Nijmegen, Netherlands

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 36期

基金：

英国工程与自然科学研究理事会;

关键词：

N-HETEROCYCLIC CARBENE; C-H ACTIVATION; STRUCTURAL-CHARACTERIZATION; BOND ACTIVATION; LIGANDS; IMIDAZOLIUM; REACTIVITY; BULKY; ASSOCIATION; PRECURSORS;

D O I：

10.1021/ja408589p

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The 'normal' three-coordinate iron-NHC complex [(IPr)Fe(N'')(2)] (N '' = N(SiMe3)(2)) rearranges to its abnormal NHC analogue [(aIPr)Fe(N '')(2)] (6) on heating, providing a rare abnormal iron-aNHC complex, and the first such three-coordinate complex. The tert-butyl-substituted complex [((IBu)-Bu-t)Fe(N")(2)] (4) undergoes a thermal decomposition that has not previously been observed in iron-NHC chemistry, resulting in the bis(imidazole) complex [((t)BuIm)(2)Fe(N '')(2)] (7). A mechanism that involves consecutive C-H and C-N activation is proposed to account for the formation of 7.

引用

页码：13338 / 13341

页数：4

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