Computational analysis of site differences in selective aliphatic C-H hydroxylation by nonheme iron-oxo complexes

Jian Wang, Yuan Yuan Zhao, Po Heng Lee

Research output: Journal article publicationJournal articleAcademic researchpeer-review

2 Citations (Scopus)


Selective C-H hydroxylation by nonheme iron complexes offers a promising method in the field of organic synthesis. Aliphatic C-H bond oxidation reactions of pivalate (R) catalyzed by [Fe(S,S-PDP)(CH3CN)2]2+(CAT1) were examined using the density functional theory. Our calculations of the CH3CN solvent agree with the experimental findings. However, it was observed that the gas-phase results did not replicate selective C-H hydroxylation observed experimentally when CAT1 catalyzed hydrocarbon oxidations by H2O2via an HO-FeVO oxidant (CAT1a). We inferred that the difference was mainly from hydrogen bonding formation, (CAT1a) O-H⋯OC (R), in certain gaseous H-abstraction transition states (TSH). Then, the appearance of the stronger (CAT1a) O-H⋯NCCH3-solvent weakened the aforementioned interaction, leading to C-H activation influenced primarily by their electronic and steric properties. Such a deduction explained the same selective C-H found in both phases of reactions with CAT1b, a cyclic ferric peracetate oxidant, by the reason of TSHwithout the influence of H-bonding. Another interesting finding was that the commonly recognized radical intermediate was further isomerized by a favorable electron rearrangement. Thus, the subsequent OH-rebound behavior proceeded by an electrostatic interaction. This study provides mechanistic clues for modifying regioselective C-H hydroxylation for molecule synthesis applications.
Original languageEnglish
Pages (from-to)13924-13930
Number of pages7
JournalPhysical Chemistry Chemical Physics
Issue number21
Publication statusPublished - 1 Jan 2017

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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