Oxidation of cyclohexane by a high-valent iron bispidine complex: a combined experimental and computational mechanistic study.

Peter Comba, Martin Maurer, Prabha Vadivelu

Journal: The journal of physical chemistry. A 2009;112(50):13028-36

PMID: 18808102

Full Text on American Chemical Society View on PubMed

Abstract

Experimental data suggest that there are various competing pathways for the catalytic and stoichiometric oxygenation of cyclohexane, assisted by iron-bispidine complexes and using various oxidants (H(2)O(2), O(2), PhIO). Density functional theory calculations indicate that both Fe(IV)=O and Fe(V)=O species are accessible and efficiently transfer their oxygen atoms to cyclohexane. The reactivities of the two isomers each and the two possible spin states for the Fe(IV)=O and Fe(V)=O species are sufficiently different to allow an interpretation of the experimental data.

Address: Universität Heidelberg, Anorganisch-Chemisches Institut, INF 270, D-69120 Heidelberg, Germany. [email protected]

DOI: 10.1021/jp8037895

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MeSH Terms: Bridged Bicyclo Compounds, Heterocyclic, Cyclohexanes, Hydrogen Peroxide, Hydroxylation, Iron, Models, Molecular, Molecular Conformation, Molecular Structure, Oxidants, Oxidation-Reduction, Oxygen