A DFT study of IRMOF-3 catalysed Knoevenagel condensation

Dario Duca, Remedios Cortese, Remedios Cortese, Dario Duca

Risultato della ricerca: Articlepeer review

24 Citazioni (Scopus)


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.
Lingua originaleEnglish
pagine (da-a)15995-16004
Numero di pagine10
RivistaPhysical Chemistry Chemical Physics
Stato di pubblicazionePublished - 2011

All Science Journal Classification (ASJC) codes

  • ???subjectarea.asjc.3100.3100???
  • ???subjectarea.asjc.1600.1606???


Entra nei temi di ricerca di 'A DFT study of IRMOF-3 catalysed Knoevenagel condensation'. Insieme formano una fingerprint unica.

Cita questo