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

Angew Chem Int Ed Engl. 2012 May 14;51(20):4887-90. doi: 10.1002/anie.201108565. Epub 2012 Apr 5.

Authors

Frederik Vermoortele¹, Matthias Vandichel, Ben Van de Voorde, Rob Ameloot, Michel Waroquier, Veronique Van Speybroeck, Dirk E De Vos

Affiliation

¹ Centre for Surface Chemistry and Catalysis, Katholieke Universiteit Leuven, Belgium.

PMID: 22488675
DOI: 10.1002/anie.201108565

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 σ(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.