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Keywords:

  • density functional calculations;
  • energetic span model;
  • hydrogen transfer;
  • iridium;
  • pincer

Abstract

A hydrogen transfer mechanism catalyzed by an IrIII PC(sp3)P pincer complex was studied by using DFT, and its efficiency was estimated by using the energetic span model. With the pristine complex, a hydrogen abstraction pathway could not be found, since a ligand dissociation to generate a vacant site is energetically costly. However, a nucleophilic attack of an alkoxide base (present in the reaction mixture) on the carbonyl ligand to form a carboalkoxy ligand generated an anionic catalyst that could easily provide the free site. From there, a hydride abstraction from an isopropyl ion (iPrO) followed by a hydride transfer to acetophenone resulted in an efficient catalytic cycle.