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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Vydáno v:Angewandte Chemie International Edition Ročník 51; číslo 20; s. 4887 - 4890
Hlavní autoři: Vermoortele, Frederik, Vandichel, Matthias, Van de Voorde, Ben, Ameloot, Rob, Waroquier, Michel, Van Speybroeck, Veronique, De Vos, Dirk E.
Médium: Journal Article
Jazyk:angličtina
Vydáno: Weinheim WILEY-VCH Verlag 14.05.2012
WILEY‐VCH Verlag
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Vydání:International ed. in English
Témata:
Carbonyl compounds
Carbonyls
Catalysis
Catalysts
Electronics
heterogeneous catalysis
Lewis acid
Lewis acidity
metal-organic framework
Metal-organic frameworks
Pictures
Samarium
structure-activity relationships
substituent effects
Unsaturated
ISSN:1433-7851, 1521-3773, 1521-3773
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Shrnutí: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).
Bibliografie:Belspo - No. IAP 6/27
ark:/67375/WNG-8R33G4WF-8
ArticleID:ANIE201108565
We are grateful to FWO, the Belspo (IAP 6/27), to KULeuven (CASAS Methusalem grant) and the Research Board of Ghent University (BOF) for project support. Funding was also received from the European Research Council under the European Community's Seventh Framework Programme [FP7(2007-2013) ERC grant agreement number 240483]. R.A. is a post-doctoral fellow of FWO. The computational resources were provided by Ghent University (Stevin Supercomputer Infrastructure).
Research Board of Ghent University
European Research Council - No. 240483
KULeuven
istex:68506CA7A77636F225F0D2F7A6F3537A90F9FB0E
FWO
We are grateful to FWO, the Belspo (IAP 6/27), to KULeuven (CASAS Methusalem grant) and the Research Board of Ghent University (BOF) for project support. Funding was also received from the European Research Council under the European Community’s Seventh Framework Programme [FP7(2007‐2013) ERC grant agreement number 240483]. R.A. is a post‐doctoral fellow of FWO. The computational resources were provided by Ghent University (Stevin Supercomputer Infrastructure).
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201108565