Carbenes in ionic liquids

被引：167

作者：

Holloczki, Oldamur ^{[2
,3
]}

Gerhard, Dirk ^{[1
]}

Massone, Klemens ^{[1
]}

Szarvas, Laszlo ^{[1
]}

Nemeth, Balazs ^{[2
]}

Veszpremi, Tazmas ^{[2
,3
]}

Nyulaszi, Laszlo ^{[2
,3
]}

机构：

[1] BASF AG, D-67056 Ludwigshafen, Germany

[2] Budapest Univ Technol & Econ, Dept Inorgan & Analyt Chem, H-1111 Budapest, Hungary

[3] Budapest Univ Technol & Econ, Hungarian Acad Sci, Mat Struct & Modeling Res Grp, H-1111 Budapest, Hungary

来源：

NEW JOURNAL OF CHEMISTRY | 2010年 / 34卷 / 12期

基金：

匈牙利科学研究基金会;

关键词：

N-HETEROCYCLIC CARBENES; NUCLEOPHILIC CARBENES; VAPOR-PRESSURE; VAPORIZATION; CHEMISTRY; BASICITY; HEXAFLUOROPHOSPHATE; SPECTROSCOPY; DIMERIZATION; MECHANISMS;

D O I：

10.1039/c0nj00380h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The chemistry of 1,3-dialkylimidazolium-based ionic liquids (ILs) can easily be linked to that of N-heterocyclic carbenes (NHCs) in the presence of sufficiently basic counteranions. B3LYP/6-31+G*, B3LYP/aug-cc-pVTZ and MP2/6-311+G** studies show that increasing the basicity of the anionic component the relative stability of the ion pair and that of the hydrogen bonded complex of the corresponding free acid and NHC itself can be shifted toward the formation of NHC. In the case of the acetate anion, the ion pair and the NHC-acetic acid complex have similar stability. Photoelectron spectroscopic studies show that the vapor of EMIM-acetate is dominated by the NHC-acetic acid complex. The mass spectrum of the same compound shows the presence of both acetic acid and 1-ethyl-3-methylimidazolium-2-ylidene, in agreement with the low pressure during the MS experiment, which facilitates dissociation. The possibility of systematic and simple variation of the NHC content of the ILs facilitates the extension of carbene chemistry in ionic liquids.

引用

页码：3004 / 3009

页数：6

共 83 条

[21] Recent developments in the organometallic chemistry of N-heterocyclic carbenes [J].