2009/10/08 by Peter Comba, Martin Maurer, Prabha Vadivelu · 1 citation
Chemistry · Materials Science · #Metal-Catalyzed Oxygenation Mechanisms #Oxidative Organic Chemistry Reactions #Porphyrin and Phthalocyanine Chemistry
paper · doi:10.1021/ic901702s
openalex publication_date 2009/10/08 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/16
The iron-bispidine-catalyzed oxidation of cyclohexane with H(2)O(2), where either a tetradentate or a pentadentate bispidine ligand is coordinated to the iron center, yields up to 35% cyclohexanol and cyclohexanone (alcohol/ketone ratio of up to 4). Product distribution (including (18)O labeling studies), kinetic isotope effects, and the ratio of tertiary/secondary alcohols with adamantane as a substrate (tertiary/secondary) suggest that (i) H abstraction by a ferryl complex is the rate-determining step and that the emerging cyclohexyl radical is short-lived, (ii) there is a parallel reaction involving oxidation by OH radicals, and (iii) there are considerable differences in the reaction pathways between the tetradentate and pentadentate ligand catalyst. These interpretations are fully supported by a DFT-based computational analysis.