Synthesis, Characterization,
and Reactivity of Hypochloritoiron(III)
Porphyrin Complexes
- Publication date
- Publisher
Abstract
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<sup>III</sup>(OCl)<sub>2</sub>]<sup>−</sup> (<b>1</b>) and the imidazole–hypochloritoiron
complexes (TPFP)Fe<sup>III</sup>(OCl)(1-R-Im) [R = CH<sub>3</sub> (<b>2</b>), H (<b>3</b>), CH<sub>2</sub>CO<sub>2</sub>H (<b>4</b>)], in which TPFP is 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinate.
The structures of <b>1</b>–<b>4</b> were confirmed
by absorption, <sup>2</sup>H and <sup>19</sup>F NMR, EPR, and resonance
Raman spectroscopy and electrospray ionization mass spectrometry at
low temperature. The reactions of <b>1</b> and <b>2</b> with various organic substrates show that <b>1</b> and <b>2</b> are capable of chlorination, sulfoxidation, and epoxidation
reactions and that <b>1</b> is much more reactive with these
substrates than <b>2</b>
