Participation of Electron Transfer Process in Rate-Limiting Step of Aromatic Hydroxylation Reactions by Compound I Models of Heme Enzymes.
Hydroxylation reactions of aromatic rings are key reactions in various biological and chemical processes. In spite of their significance, no consensus mechanism has been established. Here we performed Marcus plot analysis for aromatic hydroxylation reactions with oxoiron(IV) porphyrin π-cation radical complexes (compound I). Although many recent studies support the mechanism involving direct electrophilic attack of compound I, the slopes of the Marcus plots indicate a significant contribution of an electron transfer process in the rate-limiting step, leading us to propose a new reaction mechanism in which the electron transfer process between an aromatic compound and compound I is in equilibrium in a solvent cage and coupled with the subsequent bond formation process.
Department of Chemistry, Graduate School of Humanities and Sciences, Nara Women's University , Kitauoyanishi, Nara 630-8506, Japan.
Maaya
M
Asaka
Department of Chemistry, Graduate School of Humanities and Sciences, Nara Women's University , Kitauoyanishi, Nara 630-8506, Japan.
Hiroshi
H
Fujii
D004579:Electron Transport; D004798:Enzymes / Q000737:chemistry* / Q000378:metabolism*; D005609:Free Radicals / Q000737:chemistry; D006418:Heme / Q000737:chemistry*; D006900:Hydroxylation; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry*
D004798:Enzymes; D005609:Free Radicals; D011166:Porphyrins; D006418:Heme; D010100:Oxygen