Dioxygen Activation by a Non-Heme Iron(II) Complex: Formation of an Iron(IV)−Oxo Complex via C−H Activation by a Putative Iron(III)−Superoxo Species
- 20 July 2010
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 132 (31), 10668-10670
- https://doi.org/10.1021/ja103903c
Abstract
Iron(III)−superoxo intermediates are believed to play key roles in oxygenation reactions by non-heme iron enzymes. We now report that a non-heme iron(II) complex activates O2 and generates its corresponding iron(IV)−oxo complex in the presence of substrates with weak C−H bonds (e.g., olefins and alkylaromatic compounds). We propose that a putative iron(III)−superoxo intermediate initiates the O2-activation chemistry by abstracting a H atom from the substrate, with subsequent generation of a high-valent iron(IV)−oxo intermediate from the resulting iron(III)−hydroperoxo species.This publication has 58 references indexed in Scilit:
- Meta‐analysis of observational studies of serum 25‐hydroxyvitamin D levels and colorectal, breast and prostate cancer and colorectal adenomaInternational Journal of Cancer, 2011
- Oxygen Activation at Mononuclear Nonheme Iron Centers: A Superoxo PerspectiveInorganic Chemistry, 2010
- Shape‐Selective Interception by Hydrocarbons of the O2‐Derived Oxidant of a Biomimetic Nonheme Iron ComplexAngewandte Chemie, 2009
- Calcium Plus Vitamin D Supplementation and the Risk of Breast CancerJNCI Journal of the National Cancer Institute, 2008
- Proton‐ and Reductant‐Assisted Dioxygen Activation by a Nonheme Iron(II) Complex to Form an Oxoiron(IV) IntermediateAngewandte Chemie, 2008
- Iron Complexes of Dendrimer-Appended Carboxylates for Activating Dioxygen and Oxidizing HydrocarbonsJournal of the American Chemical Society, 2008
- Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstractionProceedings of the National Academy of Sciences of the United States of America, 2007
- Cancer survival is dependent on season of diagnosis and sunlight exposureInternational Journal of Cancer, 2006
- Evidence for C–H cleavage by an iron–superoxide complex in the glycol cleavage reaction catalyzed by myo -inositol oxygenaseProceedings of the National Academy of Sciences of the United States of America, 2006
- Vitamin D3from sunlight may improve the prognosis of breast-, colon- and prostate cancer (Norway)Cancer Causes & Control, 2004