MCD spectra of iron-sulfur complexes with or without inorganic sulfur

Tsugufumi Muraoka, Tsunenori Nozawa, Masahiro Hatano
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引用次数: 6

Abstract

The magnetic circular dichroism spectra were observed for various iron-sulfur complexes with and without inorganic sulfur as models for rubredoxin and 2-Fe ferredoxin. The MCD band shapes ascribed the bands around 390 and 490 nm to Faraday A terms for mononuclear iron sulfur complexes. These bands are probably assigned to the charge-transfer transitions from the thiol sulfur orbital to the iron t2 and e 3d-orbitals, respectively. The MCD magnitudes decreased by more than one-half for binuclear iron-sulfur complexes with inorganic sulfur in comparison with those for the mononuclear complexes. The low MCD magnitude as well as the possible core symmetry as low as D2d attributed the MCD bands to Faraday B terms. Incorporation of inorganic sulfur produced new MCD bands, some of which can be assigned to the charge-transfer transitions from the inorganic sulfur orbital to the iron t2 and e 3d-orbitals. Among complexes studied here, the bis(o-xylyldithiolato) ferrate(III) monoanion gave the MCD spectrum which resembles that of a rubredoxin. This implies that the MCD spectroscopy also assessed the complex as a good rubredoxin model. However, the binuclear complex bis[o-xylyldithiolato-μ2-sulfidoferrate(III)] dianion failed to offer the MCD spectrum similar to that of the spinach ferredoxin.

含或不含无机硫的铁硫配合物的MCD光谱
以含无机硫和不含无机硫的铁硫配合物为模型,对红氧还蛋白和2-Fe铁氧还蛋白的磁性圆二色光谱进行了观察。MCD波段形状将390和490 nm左右的波段归因于单核铁硫配合物的法拉第A项。这些带可能分别属于从硫醇硫轨道到铁t2和铁e 3d轨道的电荷转移跃迁。与单核铁硫配合物相比,含无机硫的双核铁硫配合物的MCD值降低了一半以上。低MCD量级以及可能低至D2d的核心对称性将MCD波段归因于法拉第B项。无机硫的加入产生了新的MCD带,其中一些可以分配到从无机硫轨道到铁t2和e 3d轨道的电荷转移跃迁。在本文所研究的配合物中,高铁酸盐(III)单阴离子的MCD谱与红霉素相似。这意味着MCD光谱也评估了配合物是一个很好的红霉素模型。然而,双核配合物双[o- xyylldithiolato -μ2- sulfidofer酸(III)] diion不能提供与菠菜铁氧化还蛋白相似的MCD光谱。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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