Challenges in modelling homogeneous catalysis: New answers from ab initio molecular dynamics to the controversy over the Wacker process

András Stirling, Nisanth N. Nair, Agustí Lledós, Gregori Ujaque

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Abstract

We present here a review of the mechanistic studies of the Wacker process stressing the long controversy about the key reaction steps. We give an overview of the previous experimental and theoretical studies on the topic. Then we describe the importance of the most recent Ab Initio Molecular Dynamics (AIMD) calculations in modelling organometallic reactivity in water. As a prototypical example of homogeneous catalytic reactions, the Wacker process poses serious challenges to modelling. The adequate description of the multiple role of the water solvent is very difficult by using static quantum chemical approaches including cluster and continuum solvent models. In contrast, such reaction systems are suitable for AIMD, and by combining with rare event sampling techniques, the method provides reaction mechanisms and the corresponding free energy profiles. The review also highlights how AIMD has helped to obtain a novel understanding of the mechanism and kinetics of the Wacker process. This journal is

Original languageEnglish
Pages (from-to)4940-4952
Number of pages13
JournalChemical Society Reviews
Volume43
Issue number14
DOIs
Publication statusPublished - Jul 21 2014

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ASJC Scopus subject areas

  • Chemistry(all)

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