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(mu-SC(6)H(4)-o-N(CH(3))(2))(NO)(2)](2) (1), {Fe(NO)(2)}(9)-{Fe(NO)(2)}(10) [Fe(mu-SC(6)H(4)-o-N(CH(3))(2))(NO)(2)](2)(-) (2), the anionic {Fe(NO)(2)}(10) [(SC(6)H(4)-o-N(CH(3))(2))Fe(NO)(2)](-) (3), and the anionic {Fe(NO)(2)}(10)-{Fe(NO)(2)}(10) [Fe(NO)(2)(mu-SC(6)H(4)-o-N(CH(3))(2))(mu-CO)Fe(NO)(2)](-) (4) with mixed CO-thiolate-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(mu-S)(mu-C)Fe] core with a shorter Fe...Fe distance of 2.5907(5) A attributed to the shorter Fe-S and Fe-C bond distances.