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Full Paper
A Theoretical Study of Hydrogen Transfer Catalyzed by an IrIII PC(sp3)P Pincer Complex
Article first published online: 9 JUN 2011
DOI: 10.1002/cctc.201100056
Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Kozuch, S. and Azerraf, C. (2011), A Theoretical Study of Hydrogen Transfer Catalyzed by an IrIII PC(sp3)P Pincer Complex. ChemCatChem, 3: 1348–1353. doi: 10.1002/cctc.201100056
Publication History
- Issue published online: 2 AUG 2011
- Article first published online: 9 JUN 2011
- Manuscript Received: 16 FEB 2011
Funded by
- Clore Israel Foundation
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.