A DFT/MM analysis of the effect of ligand substituents on asymmetric hydrogenation catalyzed by rhodium complexes with phosphine-phosphinite ligands

Steven M.A. Donald, Anton Vidal-Ferran, Feliu Maseras

Research output: Contribution to journalArticleResearchpeer-review

26 Citations (Scopus)

Abstract

DFT and DFT/MM calculations are carried out on the rate-determining step of the addition of dihydrogen to methyl-(N)-acetylaminoacrylate catalyzed by a rhodium catalyst containing a bidentate phosphine-phosphinite ligand. DFT calculations reproduce the experimental results, while DFT/MM calculations do not. The failure of DFT/MM methods for this particular problem is analyzed through a series of calculations with different partitions between the DFT and MM regions, which show that electronic effects of all ligand substituents considered are critical. The analysis of these electronic effects provides key information on the role of each of the substituents in the outcome of the overall catalytic process.
Original languageEnglish
Pages (from-to)1273-1279
JournalCanadian Journal of Chemistry
Volume87
Issue number10
DOIs
Publication statusPublished - 1 Oct 2009

Keywords

  • Asymmetric hydrogenation
  • Density functional theory
  • Enantioselectivity
  • Quantum mechanics/molecular mechanics methods

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