Dinuclear [{Fe(NO)2}10-{Fe(NO)2} 10] dinitrosyl iron complex with thiolate-CO-bridged ligands

Air-sensitive complexes {Fe(NO)2}9-{Fe(NO) 2}9 [Fe(μ-SC6H4o-N(CH 3)2)(NO)2]2 (1), {Fe(NO) 2}9-{Fe(NO)2}10 [Fe(μ-SC 6H4o-N(CH3)2)(NO)2] 2- (2), the anionic (Fe(NO)2}10 (SC 6H4-ON(CH3)2)Fe(NO) 2]- (3), and the anionic {Fe(NO)2} 10-(Fe(NO)2)10 [Fe(NO)2(μ-SC 6H4-o-N(CH3)2)(μ-CO)Fe(NO) 2]- (4) with mixed COthiolate-bridged ligands were synthesized. All complexes were characterized by IR, UV-vis, electron paramagnetic resonance, and single-crystal X-ray diffraction. The interconversions among these complexes were demonstrated. The interconversion between complexes 1 and 2 Is accomplished by reduction and oxidation. Complex 3 adapts a {Fe(NO)2}10 electronic structure with a N/S ligation mode and serves as a donor reagent of the {Fe(NO)2} 10 moiety. {Fe(NO)2}10-{Fe(NO) 2}10 complex 4 possesses the butterfly-like [Fe(μ-S)(μ-C)Fe] core with a shorter Fe⋯Fe distance of 2.5907(5) Å attributed to the shorter Fe-S and Fe-C bond distances.