Abstract
In this research, reaction of [Fe4(C3H3N2)4(NO)8] (1) with phenoxide and nitrite led to the formation of [(C3H3N2)(OPh)Fe(NO)2]- (2) and [(C3H3N2)(NO2)Fe(NO)2]- (3’), respectively. Synthesis of the anionic {Fe(NO)2}9 [(C3H3N2)(OPh)Fe(NO)2]- (2) supports the existence of protein-bound NHis/OTyr-DNICs. Reaction of complex 2 and thiol or thiolate in 1:1 molar ratio led to the formation of [(C3H3N2)(SPh)Fe(NO)2]- with mixed imidazolate-/thiolate- coordinated ligands. Addition of another 1 equivalent of thiol or thiolate into imidazolate-/thiolate- coordinated DNIC yielded [(SPh)2Fe(NO)2]- . These reactions elucidate the binding ability of {Fe(NO)2} moiety toward thiolate, imidazolate and phenoxide. The non-classical six-coordinated DNIC{Fe(NO)2}9 [(C3H4N2)2(η2-ONO)Fe(NO)2] [18-crown-6-ether]2 (3) was synthesized. The proposed precursor of complex 3, [(C3H3N2)(NO2)Fe(NO)2]- (3’) with EPR g value 2.03, transforms into complex 2 upon addition of 2 equivalent of phenoxide into it.