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A Theoretical Study of Hydrogen Transfer Catalyzed by an IrIII PC(sp3)P Pincer Complex

Authors

  • Dr. Sebastian Kozuch,

    Corresponding author
    1. Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem (Israel)
    2. Present Address: Department of Organic Chemistry, The Weizmann Institute of Science, IL-76100 Rehovot (Israel)
    • Institute of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem (Israel)

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  • Dr. Clarite Azerraf

    1. Institute of Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem (Israel)
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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.

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