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Issue 35, 2011
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A DFT study of IRMOF-3 catalysed Knoevenagel condensation

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It has been recently reported that IRMOF-3 [Gascon et al., J. Catal, 2009, 261, 75] may behave as a basic catalyst, active in the Knoevenagel condensation. In particular, it has been shown that the basicity of aniline-like amino moieties is enhanced, along with the catalytic activity, when incorporated into MOF structures. The computational study here was aimed at finding possible atomistic explanations of the increased basicity and catalytic activity of the IRMOF-3 embedded aniline groups, experimentally claimed. It was, moreover, aimed at guessing a reaction mechanism for the IRMOF-3 catalysed Knoevenagel condensation of benzaldehyde and ethyl-cyanoacetate. Within the DFT framework we have studied structure and basicity properties of IRMOF-3 and we have analysed the energetics of the catalytic cycle as well as of possible deactivation paths, including it. The increased basicity of IRMOF-3 over other amminic catalysts has been explained via the formation of protonated conjugate derivatives, involving hydrogen-bonds and originating quasi-planar 6-term rings. Several plausibile reaction steps have been moreover taken into account and a mechanism for the Knoevenagel condensation, including catalyst deactivation, has been proposed for aniline molecules and embedded aniline moieties. This allowed us to suggest that the increased IRMOF-3 activity, as a basic catalyst, should be mostly related to its water adsorption ability, preserving the properties of the catalytically active amino moieties.

Graphical abstract: A DFT study of IRMOF-3 catalysed Knoevenagel condensation

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Article information

23 Apr 2011
11 Jul 2011
First published
03 Aug 2011

Phys. Chem. Chem. Phys., 2011,13, 15995-16004
Article type

A DFT study of IRMOF-3 catalysed Knoevenagel condensation

R. Cortese and D. Duca, Phys. Chem. Chem. Phys., 2011, 13, 15995
DOI: 10.1039/C1CP21301F

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