A Convenient Route to Synthetic Analogues of the Oxidized Form of High-Potential Iron–Sulfur Proteins
- Kazuki Tanifuji ,
- Norihiro Yamada ,
- Tomoyuki Tajima ,
- Takahiro Sasamori ,
- Norihiro Tokitoh ,
- Tsukasa Matsuo ,
- Kohei Tamao ,
- Yasuhiro Ohki , and
- Kazuyuki Tatsumi
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† Department of Chemistry, Graduate School of Science, and Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan
‡ Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
§ Functional Elemento-Organic Chemistry Unit, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
∥ Department of Applied Chemistry, Faculty of Science and Engineering, Kinki University, 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan
*E-mail: [email protected]
Abstract
An amide-bound [Fe4S4]3+ cluster, [Fe4S4{N(SiMe3)2}4]− (1), was found to serve as a convenient precursor for synthetic analogues of the oxidized form of high-potential iron–sulfur proteins. Treatment of 1 with 4 equiv of bulky thiols led to replacement of the amide ligands with thiolates, giving rise to a series of [Fe4S4(SR)4]− clusters (R = Dmp (2a), Tbt (2b), Eind (2c), Dxp (2d), Dpp (2e); Dmp = 2,6-di(mesityl)phenyl, Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl, Dxp = 2,6-di(m-xylyl)phenyl, Dpp = 2,6-diphenylphenyl). These clusters were characterized by the mass spectrum, the EPR spectrum, and X-ray crystallography. The redox potentials of the [Fe4S4]3+/2+ couple, −0.82 V (2a), −0.86 V (2b), −0.84 V (2c), −0.74 V (2d), and −0.63 V (2e) vs Ag/Ag+ in THF, are significantly more negative than that of [Fe4S4(SPh)4]−/2– (−0.21 V).
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