Oxidative N-dealkylation reactions by oxoiron(IV) complexes of nonheme and heme ligands.
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.
Nehru
Kasi
K
Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea.
Seo
Mi Sook
MS
Kim
Jinheung
J
Nam
Wonwoo
W
D006418:Heme / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D046911:Macromolecular Substances / Q000737:chemistry; D015394:Molecular Structure; D019159:Nonheme Iron Proteins / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*
D008024:Ligands; D046911:Macromolecular Substances; D019159:Nonheme Iron Proteins; D006418:Heme; D007501:Iron; D010100:Oxygen