Institute for Molecular Science and Okazaki Institute for Integrative Bioscience, National Institutes of Natural Sciences, Myodaiji, Okazaki 444-8787, Japan.
J Am Chem Soc. 2012 Dec 26;134(51):20617-20. doi: 10.1021/ja3108774. Epub 2012 Dec 13.
A hypochloritoiron(III) porphyrin species has been proposed as a key intermediate in an antimicrobial defense system in neutrophils and in heme-catalyzed chlorination reactions. We report herein the preparation, spectroscopic characterization, and reactivity of the bis(hypochlorito)iron(III) porphyrin complex (TPFP)Fe(III)(OCl)(2) (1) and the imidazole-hypochloritoiron complexes (TPFP)Fe(III)(OCl)(1-R-Im) [R = CH(3) (2), H (3), CH(2)CO(2)H (4)], in which TPFP is 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinate. The structures of 1-4 were confirmed by absorption, (2)H and (19)F NMR, EPR, and resonance Raman spectroscopy and electrospray ionization mass spectrometry at low temperature. The reactions of 1 and 2 with various organic substrates show that 1 and 2 are capable of chlorination, sulfoxidation, and epoxidation reactions and that 1 is much more reactive with these substrates than 2.
一种次氯酸高铁卟啉物种被认为是中性粒细胞中抗菌防御系统和血红素催化的氯化反应中的关键中间体。我们在此报告了双（次氯酸根）高铁卟啉配合物[(TPFP)Fe(III)(OCl)(2)]-（1）和咪唑-次氯酸高铁配合物(TPFP)Fe(III)(OCl)(1-R-Im) [R = CH(3) (2), H (3), CH(2)CO(2)H (4)]的制备、光谱表征和反应性，其中 TPFP 是 5,10,15,20-四(五氟苯基)卟啉。1-4 的结构通过低温下的吸收、(2)H 和 (19)F NMR、EPR 和共振拉曼光谱以及电喷雾电离质谱得到证实。1 和 2 与各种有机底物的反应表明，1 和 2 能够进行氯化、氧化和环氧化反应，并且 1 比 2 更能与这些底物反应。
