1206554-92-8Relevant articles and documents
Hydrosulfide (HS-) coordination in iron porphyrinates
Pavlik, Jeffrey W.,Noll, Bruce C.,Oliver, Allen G.,Schulz, Charles E.,Robert Scheldt
, p. 1017 - 1026 (2010)
Recent reports of potential physiological roles of hydrogen sulfide have prompted interest in heme-sulfide interactions. Heme - H2S and/or heme - HS- interactions could potentially occur during endogenous production, transport, signaling events, and catabolism of H2S. We have investigated the interaction of the hydrosulfide ion (HS-) with iron porphyrinates. UV - vis spectral studies show the formation of [Fe(Por(SH)]-, [Fe(Por)(SH)2]2-, and the mixed-ligand species [Fe(Por(Im)(SH)]-. UV - vis binding studies of [Fe(OEP) and [Fe(T-p-OMePP)] (OEP = octaethylporphyrinate; T-p-OMePP = tetra-p-methoxyphenylporphyrinate) with HS- allowed for calculation of the formation constants and extinction coefficients of mono- and bis-HS - complexes. We report the synthesis of the first HS --bound iron(II) porphyrin compounds, [Na(222)][Fe(OEP)(SH)] ·0.5C6H6 and [Na(222)][Fe(T-ρ-OMePP)(SH) ·C6H5Cl (222 = Kryptofix-222). Characterization by single-crystal X-ray analysis, mass spectrometry, and Moessbauer and IR spectroscopy is all consistent with that of known sulfur-bound high-spin iron(II) compounds. The Fe - S distances of 2.3929(5) and 2.3887(13) A are longer than all reported values of [FeII(Por)(SR)]- species. An analysis of the porphyrin nonplanarity for these derivatives and for all five-coordinate high-spin iron(II) porphyrinate derivatives with an axial anion ligand is presented. In our hands, attempts to synthesize iron(III) HS- derivatives led to iron(II) species.
