Oxidative N-Dealkylation Reactions by Oxoiron(IV) Complexes of Nonheme and Heme Ligands
- 2 December 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 46 (1) , 293-298
- https://doi.org/10.1021/ic0614014
Abstract
Nonheme and heme iron monooxygenases participate in oxidative N-dealkylation reactions in nature, and high-valent oxoiron(IV) species have been invoked as active oxidants that effect the oxygenation of organic substrates. The present study describes the first example of the oxidative N-dealkylation of N,N-dialkylamines by synthetic nonheme oxoiron(IV) complexes and the reactivity comparisons of nonheme and heme oxoiron(IV) complexes. Detailed mechanistic studies were performed with various N,N-dialkylaniline substrates such as para-substituted N,N-dimethylanilines, para-chloro-N-ethyl-N-methylaniline, para-chloro-N-cyclopropyl-N-isopropylaniline, and deuteriated N,N-dimethylanilines. The results of a linear free-energy correlation, inter- and intramolecular kinetic isotope effects, and product analysis studied with the mechanistic probes demonstrate that the oxidative N-dealkylation reactions by nonheme and heme oxoiron(IV) complexes occur via an electron transfer-proton transfer (ET-PT) mechanism.Keywords
This publication has 61 references indexed in Scilit:
- Mechanistic Studies of the Oxidative N-Dealkylation of a Substrate Tethered to Carboxylate-Bridged Diiron(II) Complexes, [Fe2(μ-O2CArTol)2(O2CArTol)2(N,N-Bn2en)2]Inorganic Chemistry, 2006
- Oxidative dealkylation DNA repair mediated by the mononuclear non-heme iron AlkB proteinsJournal of Inorganic Biochemistry, 2006
- Oxoiron(IV) porphyrin π-cation radical complexes with a chameleon behavior in cytochrome P450 model reactionsJBIC Journal of Biological Inorganic Chemistry, 2005
- Thermodynamics and kinetics of proton-coupled electron transfer: stepwise vs. concerted pathwaysBiochimica et Biophysica Acta (BBA) - Bioenergetics, 2003
- First Direct Evidence for Stereospecific Olefin Epoxidation and Alkane Hydroxylation by an Oxoiron(IV) Porphyrin ComplexJournal of the American Chemical Society, 2003
- Mechanisms of Hydrogen-, Oxygen-, and Electron-Transfer Reactions of Cumylperoxyl RadicalJournal of the American Chemical Society, 2003
- Oxidative N-Dealkylation of a Carboxylate-Bridged Diiron(II) Precursor Complex by Reaction with O2 Affords the Elusive {Fe2(μ-OH)2(μ-O2CR)}3+ Core of Soluble Methane Monooxygenase HydroxylaseJournal of the American Chemical Society, 2001
- Mechanisms of N-Demethylations Catalyzed by High-Valent Species of Heme Enzymes: Novel Use of Isotope Effects and Direct Observation of IntermediatesJournal of the American Chemical Society, 1998
- Kinetic Deuterium Isotope Effect Profiles and Substituent Effects in the Oxidative N-Demethylation of N,N-Dimethylanilines Catalyzed by Tetrakis(pentafluorophenyl)porphyrin Iron(III) ChlorideJournal of the American Chemical Society, 1998
- Nonheme Iron Centers in Oxygen Activation: Characterization of an Iron(III) Hydroperoxide IntermediateAngewandte Chemie International Edition in English, 1995