NHC catalyzed CO2 fixation with epoxides: Probable mechanisms reveal ter molecular pathway

被引：50

作者：

Ajitha, Manjaly J. ^{[1
]}

Suresh, Cherumuttathu H. ^{[1
]}

机构：

[1] Natl Inst Interdisciplinary Sci & Technol CSIR, Computat Modeling & Simulat Sect, Trivandrum, Kerala, India

来源：

TETRAHEDRON LETTERS | 2011年 / 52卷 / 41期

关键词：

NHC catalysis; CO2; fixation; Density functional theory; Reaction mechanism; Ter molecular pathway; N-HETEROCYCLIC CARBENE; CARBON-DIOXIDE; AROMATIC-ALDEHYDES; METHANOL; ORGANOCATALYSTS; TRANSFORMATION; CARBOXYLATES; CONVERSION;

D O I：

10.1016/j.tetlet.2011.08.062

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Six different pathways for the NHC-mediated CO2 transformation reaction of epoxide to cyclic carbonate are investigated with DFT method at MPWB1K/6-311++G(3df,2p) level which confirms that the most favorable pathway is ter molecular in nature and passes through a regioselective S(N)2 anti-attack of NHC on the least substituted carbon of the epoxide-CO2 complex. (C) 2011 Elsevier Ltd. All rights reserved.

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页码：5403 / 5406

页数：4

相关论文

共 28 条

[1] Utilisation of CO2 as a chemical feedstock:: opportunities and challenges [J].

Aresta, Michele ;

Dibenedetto, Angela .

DALTON TRANSACTIONS, 2007, (28) :2975-2992

[2] High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture [J].

Banerjee, Rahul ;

Phan, Anh ;

Wang, Bo ;

Knobler, Carolyn ;

Furukawa, Hiroyasu ;

O'Keeffe, Michael ;

Yaghi, Omar M. .

SCIENCE, 2008, 319 (5865) :939-943

[3] Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides, and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity [J].

Bhanage, BM ;

Fujita, S ;

Ikushima, Y ;

Arai, M .

APPLIED CATALYSIS A-GENERAL, 2001, 219 (1-2) :259-266

[4] CARBON-MONOXIDE AND CARBON-DIOXIDE FIXATION - RELEVANT C-1 AND C-2 LIGAND REACTIONS EMPHASIZING (ETA-5-C5H5)FE-CONTAINING COMPLEXES [J].

CUTLER, AR ;

HANNA, PK ;

VITES, JC .

CHEMICAL REVIEWS, 1988, 88 (07) :1363-1403

[5] N-Heterocyclic Carbenes in Late Transition Metal Catalysis [J].

Diez-Gonzalez, Silvia ;

Marion, Nicolas ;

Nolan, Steven P. .

CHEMICAL REVIEWS, 2009, 109 (08) :3612-3676

[6] Reversible carboxylation of N-heterocyclic carbenes [J].

Duong, HA ;

Tekavec, TN ;

Arif, AM ;

Louie, J .

CHEMICAL COMMUNICATIONS, 2004, (01) :112-113

[7]

Frisch M., 2004, GAUSSIAN 03 REVISION, DOI DOI 10.1016/J.MOLSTRUC.2017.03.014

[8] Unexpected CO2 Splitting Reactions To Form CO with N-Heterocyclic Carbenes as Organocatalysts and Aromatic Aldehydes as Oxygen Acceptors [J].

Gu, Liuqun ;

Zhang, Yugen .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (03) :914-+

[9] Heterocyclic carbenes: Synthesis and coordination chemistry [J].

Hahn, F. Ekkehardt ;

Jahnke, Mareike C. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (17) :3122-3172

[10] 1,3-dimethylimidazolium-2-carboxylate:: the unexpected synthesis of an ionic liquid precursor and carbene-CO2 adduct [J].

Holbrey, JD ;

Reichert, WM ;

Tkatchenko, I ;

Bouajila, E ;

Walter, O ;

Tommasi, I ;

Rogers, RD .

CHEMICAL COMMUNICATIONS, 2003, (01) :28-29