Synthesis, Characterization, and Reactivity of Hypochloritoiron(III) Porphyrin Complexes

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• 作者：Zhiqi Cong ; Sachiko Yanagisawa ; Takuya Kurahashi ; Takashi Ogura ; Satoru Nakashima ; Hiroshi Fujii
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：December 26, 2012
• 年：2012
• 卷：134
• 期：51
• 页码：20617-20620
• 全文大小：300K
• 年卷期：v.134,no.51(December 26, 2012)
• ISSN：1520-5126

文摘

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]^{鈭?/sup> (1) and the imidazole鈥揾ypochloritoiron complexes (TPFP)FeIII(OCl)(1-R-Im) [R = CH₃ (2), H (3), CH₂CO₂H (4)], in which TPFP is 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinate. The structures of 1鈥?b>4 were confirmed by absorption, 2H and 19F 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.}