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

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

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 σm values of the linker substituents X and the rate kX of a carbonyl‐ene reaction. This...

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Veröffentlicht in:Angewandte Chemie International Edition 2012-05, Vol.51 (20), p.4887-4890
Hauptverfasser: Vermoortele, Frederik, Vandichel, Matthias, Van de Voorde, Ben, Ameloot, Rob, Waroquier, Michel, Van Speybroeck, Veronique, De Vos, Dirk E.
Format: Artikel
Sprache:eng
Schlagworte:
Carbonyls
Catalysis
Catalysts
Electronics
heterogeneous catalysis
Lewis acid
Lewis acidity
metal-organic framework
Metal-organic frameworks
Pictures
Samarium
structure-activity relationships
substituent effects
Unsaturated
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Zusammenfassung: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 σm values of the linker substituents X and the rate kX 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).
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201108565