A three states model for hydrogen abstraction reactions with the cytochrome P450 compound I is revisited. Isolobal and isospin analogy among Fe(IV)=O, O = O and O

• Published in: Journal of photochemistry and photobiology. A, Chemistry. Chemistry., 2021-01, Vol.405, p.112902, Article 112902
• Main Authors: Miyagawa, Koichi, Isobe, Hiroshi, Shoji, Mitsuo, Kawakami, Takashi, Yamanaka, Shusuke, Yamaguchi, Kizashi
• Format: Article
• Language: English
• Subjects: Beyond DFT; Broken Symmetry; Compound I; Diradical mechanism; Fe(V)=O; Hybrid DFT; Hydroxylation
• ISSN: 1010-6030; 1873-2666
• DOI: 10.1016/j.jphotochem.2020.112902

[Display omitted] •Three states model of the compound I in P450.•Total doublet spin state is not only 2CpdIa but also 2CpdIb.•2CpdIa is 2{2[↓• +Por]-3[↑• Fe(IV)=O •↑]}.•2CpdIb is 2{1[Por]-2[↑• Fe(V)=O]}.•Hydrogen abstraction reaction proceeds through the formations of 2CpdIb and the oxyl-radical species (2CpdIb,oxyl). Radical abstraction reactions by the cytochrome P450 compound I are investigated on the basis of the one quartet two doublet model consisted of three configurations; 4{2[↑• +Por]–[↑• 3Fe(IV)=O •↑]} (4CpdI; S = 3/2), 2{2[↓• +Por]–[↑• 3Fe(IV)=O •↑]} (2CpdIa; S = 1/2) and 2{1[Por(↑↓)]–2[↑• Fe(V)=O]} (2CpdIb; S = 1/2) where Por denotes porphyrin and axial cysteine anion (–SR) is neglected. The dπ-pπ bond of 2CpdIb was highly spin-polarized in the transition-state region of hydrogen abstraction reactions, providing the doublet configuration; 2{1[Por(↑↓)]–2[↑↑•• Fe(IV)–O •↓]} (2CpdIb,oxyl). The oxyl-radical character of 2CpdIb,oxyl plays an important role for hydrogen radical abstraction from alkanes. The spin populations on the iron atom at the transition structures by available density functional theory (DFT) results were about 2.0 for 2CpdIb,oxyl, whereas they were about 1.0 for 4CpdI and 2CpdIa. On the other hand, the spin density population on the carbon atom of alkyl radical were negative and positive in sign for 2CpdIb,oxyl and 4CpdI, respectively, in consistent with their spin structures. In order to elucidate possible reaction pathways by the cytochrome P450 compound I, relative stabilities between 4CpdI and 2CpdIb were examined on the basis of available DFT and beyond DFT results. The refined DFT results obtained by the beyond DFT elucidated one of the possible reaction pathways for hydrogen abstractions; 2CpdIa → 2Cpdb → 2CpdIb,oxyl → 2(TS) → (rebound). Implications of the computational results are also discussed in relation to water oxidation in artificial catalysts.