TY - JOUR
T1 - A convenient route to synthetic analogues of the oxidized form of high-potential iron-sulfur proteins
AU - Tanifuji, Kazuki
AU - Yamada, Norihiro
AU - Tajima, Tomoyuki
AU - Sasamori, Takahiro
AU - Tokitoh, Norihiro
AU - Matsuo, Tsukasa
AU - Tamao, Kohei
AU - Ohki, Yasuhiro
AU - Tatsumi, Kazuyuki
PY - 2014/4/21
Y1 - 2014/4/21
N2 - 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).
AB - 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).
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U2 - 10.1021/ic402890k
DO - 10.1021/ic402890k
M3 - Article
C2 - 24694068
AN - SCOPUS:84899419684
SN - 0020-1669
VL - 53
SP - 4000
EP - 4009
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 8
ER -