Hydrosulfide (HS-) coordination in iron porphyrinates.
Hydrosulfide (HS-) coordination in iron porphyrinates.
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DOI：
10.1021/ic901853p
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发表时间：
2010-02-01
影响因子：
4.6
通讯作者：
Scheidt, W. Robert
中科院分区：
文献类型：
--
作者：
Pavlik, Jeffrey W.;Noll, Bruce C.;Oliver, Allen G.;Schulz, Charles E.;Scheidt, W. Robert
最近关于硫化氢的潜在生理作用的报道引起了人们对血红素-硫化物相互作用的兴趣。血红素-H2S和/或血红素-HS −相互作用可能发生在H2S的内源性产生、运输、信号事件和催化过程中。我们研究了硫氢根离子（HS-）与铁卟啉的相互作用。紫外-可见光谱研究表明形成了[Fe（Por）（SH）]−、[Fe（Por）（SH）2]2−和混合配体物种[Fe（Por）（Im）（SH）]−。[Fe（OEP）]和[Fe（Tp-OMePP）]（OEP =八乙基卟啉盐，Tp-OMePP =四对甲氧基苯基卟啉盐）与HS−的紫外-可见结合研究允许计算单和双HS −络合物的形成常数和消光系数。我们报道了第一个HS-结合铁卟啉化合物[Na（222）][Fe（OEP）（SH）]·0.5C6H6和[Na（222）][Fe（Tp-OMePP）（SH）]·C6 H5 Cl（222 = kryptofix-222）的合成。单晶X射线分析、质谱、穆斯堡尔谱和红外光谱的表征都与已知的硫结合的高自旋铁（II）化合物一致。Fe-S距离为2.3929（5）和2.3887（13）<$m，比所有报道的[Fe II（Por）（SR）]−物种的值都长。卟啉非平面性的分析，这些衍生物和所有五个坐标的高自旋铁（II）卟啉衍生物与轴向阴离子配体。在我们的手中，试图合成铁（III）HS−衍生物导致铁（II）物种。
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(Tp-OMePP)] (OEP = octaethylporphyrinate, Tp-OMePP = tetra-p-methoxyphenylporphyrinate) with HS− allowed for calculation of formation constants and extinction coefficients of the 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(Tp-OMePP)(SH)]·C6H5Cl (222 = kryptofix-222). Characterization by single-crystal X-ray analysis, mass spectrometry, and Mössbauer and IR spectroscopy are 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) Å are longer than all reported values of [FeII(Por)(SR)]− species. An analysis of porphyrin non-planarity 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.
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影响因子：
4.6
作者：
Chatwin, SL;Diggle, RA;Whittlesey, MK
通讯作者：
Whittlesey, MK
影响因子：
56.9
作者：
Blackstone, E;Morrison, M;Roth, MB
通讯作者：
Roth, MB
影响因子：
4.6
作者：
GAFFNEY, TR;IBERS, JA
通讯作者：
IBERS, JA
影响因子：
15
作者：
CAI, LS;HOLM, RH
通讯作者：
HOLM, RH
影响因子：
1.6
作者：
DOELLER, JE;KRAUS, DW;WITTENBERG, JB
通讯作者：
WITTENBERG, JB