Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks

被引：379

作者：

Vermoortele, Frederik ^{[2
]}

Vandichel, Matthias ^{[1
]}

Van de Voorde, Ben ^{[2
]}

Ameloot, Rob ^{[2
]}

Waroquier, Michel ^{[1
]}

Van Speybroeck, Veronique ^{[1
]}

De Vos, Dirk E. ^{[2
]}

机构：

[1] Univ Ghent, Ctr Mol Modeling, B-9052 Zwijnaarde, Belgium

[2] Katholieke Univ Leuven, Ctr Surface Chem & Catalysis, B-3001 Louvain, Belgium

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2012年 / 51卷 / 20期

基金：

欧洲研究理事会;

关键词：

heterogeneous catalysis; Lewis acidity; metal-organic framework; structure-activity relationships; substituent effects; ASYMMETRIC CATALYSTS; CARBON-DIOXIDE; EPOXIDATION; ADSORPTION; SEPARATION; MIL-47; SITES;

D O I：

10.1002/anie.201108565

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Functionalized linkers can greatly increase the activity of metal-organic framework (MOF) catalysts with coordinatively unsaturated sites. A clear linear free-energy relationship (LFER) was found between Hammett m values of the linker substituents X and the rate k X of a carbonyl-ene reaction. This is the first LFER ever observed for MOF catalysts. A 56-fold increase in rate was found when the substituent is a nitro group (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：4887 / 4890

页数：4

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