Novel Rubredoxin Model Tetrathiolato Iron(II) and Cobalt(II) Complexes Containing Intramolecular Single and Double NH.S Hydrogen Bonds.

Simple rubredoxin model complexes with o-(acylamino)benzenethiolato and 2,6-(diacylamino)benzenethiolato were synthesized and characterized by (1)H NMR, IR, and electrochemical properties. The structures of (NEt(4))(2)[Fe(II)(S-o-t-BuCONHC(6)H(4))(4)].2EtCN (3a), (NEt(4))(2)[Co(II)(S-o-t-BuCONHC(6)H(4))(4)].2EtCN (3b), and (PPh(4))(2)[Co(II){S-2,6-(CF(3)CONH)(2)C(6)H(3)}(4)].Et(2)O (5b') were determined by X-ray analysis. The complexes have intramolecular single or double NH.S hydrogen bonds. The mean Fe-S and Co-S distances are significantly shorter than those of non-hydrogen-bonding complexes, [M(SPh)(4)](2-) (M = Fe(II), Co(II)), by 0.024 Å (3a), 0.032 Å (3b), and 0.029 Å (5b'), respectively. (NMe(4))(2)[Fe(II)(S-o-CH(3)CONHC(6)H(4))(4)] (2a) and (NMe(4))(2)[Fe(II){S-2,6-(CH(3)CONH)(2)C(6)H(3)}(4)] (6a) have remarkably positive shifted Fe(III)/Fe(II) redox couples by the single and double NH.S hydrogen bond, respectively. The shifts are +0.25 for 2a and +0.56 for 6a from the redox potential of [Fe(II)(SPh)(4)](2-), which indicate additivity of the effect of the NH.S hydrogen bond. The formation and the structure of a novel chelating amido(thiolato) complex (PPh(4))(2)[Co(II){S-2,6-(CF(3)CONH)(2)C(6)H(3)}(2)(S-2-CF(3)CONH-6-CF(3)CONC(6)H(3))].Et(2)O (9) are also described.