Functional Model of Compound II of Cytochrome P450: Spectroscopic Characterization and Reactivity Studies of a FeIV–OH Complex

化学 反应性(心理学) 氧化还原 配体(生物化学) 氧化剂 电子转移 金属 药物化学 协调球 立体化学 氧化态 结晶学 光化学 无机化学 有机化学 病理 受体 替代医学 医学 生物化学
作者
Kritika Keshari,Aakash Santra,Lucía Velasco,Maxime Sauvan,Simarjeet Kaur,Ashok D. Ugale,Sandip Munshi,José F. Marco,Dooshaye Moonshiram,Sayantan Paria
出处
期刊:JACS Au [American Chemical Society]
卷期号:4 (3): 1142-1154
标识
DOI:10.1021/jacsau.3c00844
摘要

Herein, we show that the reaction of a mononuclear FeIII(OH) complex (1) with N-tosyliminobenzyliodinane (PhINTs) resulted in the formation of a FeIV(OH) species (3). The obtained complex 3 was characterized by an array of spectroscopic techniques and represented a rare example of a synthetic FeIV(OH) complex. The reaction of 1 with the one-electron oxidizing agent was reported to form a ligand-oxidized FeIII(OH) complex (2). 3 revealed a one-electron reduction potential of −0.22 V vs Fc+/Fc at −15 °C, which was 150 mV anodically shifted than 2 (Ered = −0.37 V vs Fc+/Fc at −15 °C), inferring 3 to be more oxidizing than 2. 3 reacted spontaneously with (4-OMe-C6H4)3C• to form (4-OMe-C6H4)3C(OH) through rebound of the OH group and displayed significantly faster reactivity than 2. Further, activation of the hydrocarbon C–H and the phenolic O–H bond by 2 and 3 was compared and showed that 3 is a stronger oxidant than 2. A detailed kinetic study established the occurrence of a concerted proton–electron transfer/hydrogen atom transfer reaction of 3. Studying one-electron reduction of 2 and 3 using decamethylferrocene (Fc*) revealed a higher ket of 3 than 2. The study established that the primary coordination sphere around Fe and the redox state of the metal center is very crucial in controlling the reactivity of high-valent Fe–OH complexes. Further, a FeIII(OMe) complex (4) was synthesized and thoroughly characterized, including X-ray structure determination. The reaction of 4 with PhINTs resulted in the formation of a FeIV(OMe) species (5), revealing the presence of two FeIV species with isomer shifts of −0.11 mm/s and = 0.17 mm/s in the Mössbauer spectrum and showed FeIV/FeIII potential at −0.36 V vs Fc+/Fc couple in acetonitrile at −15 °C. The reactivity studies of 5 were investigated and compared with the FeIV(OH) complex (3).

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