REDOX BEHAVIOR OF 4FE-4S FERREDOXIN MODEL ARENETHIOLATE COMPLEXES INVOLVING SPECIFIC NH-CENTER-DOT-CENTER-DOT-CENTER-DOT-S HYDROGEN-BONDS ASSISTED BY A NEIGHBORING PHENYL GROUP
T. Ueno et al., REDOX BEHAVIOR OF 4FE-4S FERREDOXIN MODEL ARENETHIOLATE COMPLEXES INVOLVING SPECIFIC NH-CENTER-DOT-CENTER-DOT-CENTER-DOT-S HYDROGEN-BONDS ASSISTED BY A NEIGHBORING PHENYL GROUP, Journal of the Chemical Society. Dalton transactions, (19), 1996, pp. 3859-3863
The complexes [NMe(4)](2)[Fe4S4(SC(6)H(3)Ph-6-NHCOR'-2)(4)](2-) (R' =
Bu(t) 1, Me 2 or CF3 3), [NMe(4)](2)[Fe4S4(SC(6)H(3)Ph-6-NHCOR'-4)(4)]
(2-) (R' = Bu(t) 4 or CF3 5) and [NMe(4)][Fe4S4(SC(6)H(3)Et-6-NHCOBu(t
)-2)(4)](2-) 6 were synthesized by ligand-exchange reactions of [NMe(4
)](2)[Fe4S4(SBu(t))(4)](2-) with the corresponding organic disulfides.
They have been characterized by IR and UV/VIS spectroscopy and by ele
mental microanalyses. From IR spectra in the solid state, the v(NH) sh
ift (114 cm(-1)) of 1 from the band of the corresponding disulfide is
larger than that of 6 (87 cm(-1)). The results indicate that the pheny
l group at the 6 position contributes to the strengthening of the NH .
.. S hydrogen bond. The stabilization of the [Fe4S4(SR)(4)](-)-[Fe4S4(
SR)(4)](2-) redox potential of 1 compared with 6 is due to the co-oper
ation of the aromatic ring and this hydrogen bond.