氧代铁（IV）卟啉的酸催化歧化反应生成氧代铁（IV）卟啉自由基阳离子。
Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations.
作者信息
Pan Zhengzheng, Newcomb Martin
机构信息
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607.
出版信息
Inorg Chem Commun. 2011 Jun 1;14(6):968-970. doi: 10.1016/j.inoche.2011.03.044.
Abstract
Disproportionation of oxoiron(IV) porphyrin (Compound II) to oxoiron(IV) porphyrin radical cation (Compound I) was studied in three P450 model systems with different electronic structures. Direct conversion of Compound II to Compound I has been observed for 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP) in acid-catalyzed reactions in a mixed solvent of acetonitrile and water (1:1, v/v) containing excess m-CPBA oxidant, with a second-order rate constant of (1.3 ± 0.2) × 10(2) M(-1) s(-1). The acid-catalyzed disproportionation heavily depends on the electron demand of the substituted aryl groups on the porphyrin macrocycle. The disproportionation equilibrium constants show drastic change for the three porphyrin systems.
摘要
在三种具有不同电子结构的P450模型体系中研究了氧代铁（IV）卟啉（化合物II）歧化为氧代铁（IV）卟啉自由基阳离子（化合物I）的过程。在含有过量间氯过氧苯甲酸氧化剂的乙腈和水（1:1，v/v）混合溶剂中进行的酸催化反应中，已观察到5,10,15,20-四（2,6-二氯苯基）卟啉（TDCPP）的化合物II直接转化为化合物I，二级速率常数为（1.3±0.2）×10² M⁻¹ s⁻¹。酸催化歧化在很大程度上取决于卟啉大环上取代芳基的电子需求。对于这三种卟啉体系，歧化平衡常数显示出剧烈变化。
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