Lee W A, Calderwood T S, Bruice T C
Proc Natl Acad Sci U S A. 1985 Jul;82(13):4301-5. doi: 10.1073/pnas.82.13.4301.
An electrochemical study of hydroxide- and methoxide-ligated iron(III) tetraphenylporphyrins possessing ortho-phenyl substituents that block mu-oxo dimer formation has been carried out. Ligation by these strongly basic oxyanions promotes the formation of iron(IV)-oxo porphyrins upon one-electron oxidation. Further one-electron oxidation of the latter provides the iron(IV)-oxo porphyrin pi-cation radical. These results are discussed in terms of chemical model studies and the enzymatic intermediate compounds I and II of the peroxidases.
对具有邻位苯基取代基以阻止μ-氧二聚体形成的氢氧化物和甲醇盐配位的铁(III)四苯基卟啉进行了电化学研究。这些强碱性氧阴离子的配位作用促进了单电子氧化时铁(IV)-氧卟啉的形成。后者进一步的单电子氧化产生铁(IV)-氧卟啉π-阳离子自由基。根据化学模型研究以及过氧化物酶的酶促中间体化合物I和II对这些结果进行了讨论。