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, Kazuyuki Tatsumi

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Abstract

An amide-bound [Fe4S4]3+ cluster, [Fe 4S4{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).

Original languageEnglish
Pages (from-to)4000-4009
Number of pages10
JournalInorganic Chemistry
Volume53
Issue number8
DOIs
Publication statusPublished - Apr 21 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Tanifuji, K., Yamada, N., Tajima, T., Sasamori, T., Tokitoh, N., Matsuo, T., Tamao, K., Ohki, Y., & Tatsumi, K. (2014). A convenient route to synthetic analogues of the oxidized form of high-potential iron-sulfur proteins. Inorganic Chemistry, 53(8), 4000-4009. https://doi.org/10.1021/ic402890k