Electronic effects of linker substitution on Lewis acid catalysis with metal-organic frameworks

Frederik Vermoortele; Matthias Vandichel; Ben Van De Voorde; Rob Ameloot; Michel Waroquier; Veronique Van Speybroeck; Dirk E. De Vos

doi:10.1002/anie.201108565

Electronic effects of linker substitution on Lewis acid catalysis with metal-organic frameworks

Frederik Vermoortele
, Matthias Vandichel
, Ben Van De Voorde
, Rob Ameloot
, Michel Waroquier
, Veronique Van Speybroeck
, Dirk E. De Vos

KU Leuven
Ghent University

Research output: Contribution to journal › Article › peer-review

Abstract

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).

Original language	English
Pages (from-to)	4887-4890
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	51
Issue number	20
DOIs	https://doi.org/10.1002/anie.201108565
Publication status	Published - 14 May 2012
Externally published	Yes

Keywords

heterogeneous catalysis
Lewis acidity
metal-organic framework
structure-activity relationships
substituent effects

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10.1002/anie.201108565

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abstract = "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).",

keywords = "heterogeneous catalysis, Lewis acidity, metal-organic framework, structure-activity relationships, substituent effects",

author = "Frederik Vermoortele and Matthias Vandichel and \{Van De Voorde\}, Ben and Rob Ameloot and Michel Waroquier and \{Van Speybroeck\}, Veronique and \{De Vos\}, \{Dirk E.\}",

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doi = "10.1002/anie.201108565",

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T1 - Electronic effects of linker substitution on Lewis acid catalysis with metal-organic frameworks

AU - Vermoortele, Frederik

AU - Vandichel, Matthias

AU - Van De Voorde, Ben

AU - Ameloot, Rob

AU - Waroquier, Michel

AU - Van Speybroeck, Veronique

AU - De Vos, Dirk E.

PY - 2012/5/14

Y1 - 2012/5/14

N2 - 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).

AB - 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).

KW - heterogeneous catalysis

KW - Lewis acidity

KW - metal-organic framework

KW - structure-activity relationships

KW - substituent effects

UR - https://www.scopus.com/pages/publications/84860855938

U2 - 10.1002/anie.201108565

DO - 10.1002/anie.201108565

M3 - Article

AN - SCOPUS:84860855938

SN - 1433-7851

VL - 51

SP - 4887

EP - 4890

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 20

ER -

Electronic effects of linker substitution on Lewis acid catalysis with metal-organic frameworks

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Keywords

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