OXOPORPHINATO-IRON(V) OXIDATION OF POLYCYCLIC AROMATICS

该项目的长期目标是提供对 同工酶家族细胞色素 P450 的单氧化机制。 实现这一目标的战略的前提是 催化活性中间体是氧代铁基卟啉阳离子 自由基（cpd I 类似物）。 遵循的方法是 表征一系列合成的氧代铁基卟啉阳离子自由基 为了确定分子和电子结构的参数并 使用氧代铁基卟啉阳离子将参数与化学关联起来 自由基作为氧化剂与选定的多环芳烃（PAH） 底物作为探针。 特别令人感兴趣的是以下影响： 铁卟啉自由基自旋耦合在化学反应中的应用 综合模型系统。 尽管模型 cpd I 类似物表现出很强的 平行（铁磁）耦合，所有已知酶物种中的耦合是 弱或反平行（反铁磁）。 虽然合成模型 不要接近酶的复杂性，会学到很多东西 关于氧代铁基卟啉阳离子自由基的化学和 该物种对 PAH 的氧化作用。 要研究的氧代铁基卟啉阳离子自由基源自 具有以下芳基取代基的四芳基卟啉铁配合物： 2,4,6-三甲基苯基（均三甲苯）； 2,4,6-三甲氧基苯基； 2,6- 二氯苯基。 此外，来自 2,4,6-三甲基苯基的 cpd I 类似物 吡咯 B 位被溴和芴取代的配合物 将被表征。 二四芳基二氢卟酚（7,8-二氢 四苯基卟啉）配合物：2,6-二氯苯基-和2,6- 双三氟甲基二氯甲烷，将根据适应症进行调查 高价络合物具有不寻常的物理化学性质。 PAH 底物是红荧烯，预计可以轻松进行单- 电子氧化成稳定的阳离子自由基、苯并蒽和苯[k] 苊菲。 后两种 PAH 应通过 1- 生成 7,12-醌 电子氧化和二氢二醇和/或酚通过亲电子 加成重排机制。

The long-term goal of this project is to provide insight into the mechanisms of monooxygenation by the family of isozymes, cytochromes P450. A premise underlying the strategy for achieving this objective is that the catalytically competent intermediates are oxoferryl prophyrin cation radicals (cpd I analogues). The approach to be followed will be to characterize a series of synthetic oxoferryl porphyrin cation radicals in order to determine parameters of molecular and electronic structure and to correlate parameters with chemistry by using the oxoferryl porphyrin cation radicals as oxidants with selected polycyclic aromatic hydrocarbon (PAH) substrates as probes. Of particular interest will be the implications of the ferryl-porphyrin radical spin coupling for chemical reactivity in the synthetic model systems. Although model cpd I analogues exhibit strong parallel (ferromagnetic) coupling, coupling in all known enzymic species is either weak or anti-parallel (antiferromagnetic). While synthetic models do not approach the complexity of the enzymes, much will be learned concerning the chemistry of oxoferryl porphyrin cation radicals and the oxidation of PAH by this species. The oxoferryl porphyrin cation radicals to be studied are derived from tetraaryl porphinatoiron complexes with the following aryl substituents: 2,4,6-trimethylphenyl (mesityl); 2,4,6-trimethoxyphenyl; 2,6- dichlorophenyl. In addition, cpd I analogues from 2,4,6-trimethlyphenyl complexes substituted on the pyrrole B-positions with bromine and fluorene will be characterized. Two tetraaryl chlorin (7,8-dihydro tetraphenylporphyrin) complexes: 2,6-dichlorophenyl-and 2,6- bistrifluoromethyl chlorin, will be investigated in light of indications that the high-valent complexes have unusual physico-chemical properties. PAH substrates are rubrene, which is expected to undergo facile one- electron oxidation to a stable cation radical, benzanthracene and benz[k] acephenanthrylene. The latter two PAH should give 7,12-quinones by one- electron oxidation and dihydrodiols and/or phenols by an electrophilic addition-rearrangement mechanism.