摘要
Transformation of {Fe(NO) 2 } 10 dinitrosyliron complex (DNIC) Fe(CO) 2 (NO) 2 into [{Fe(NO) 2 } 9 ] 2 Roussin's red ester (RRE) [(μ-S(CH 2 ) 2 NH 2 )Fe(NO) 2 ] 2 (3) triggered by cysteamine via the reaction pathway (intermediates) [{Fe(NO) 2 } 10 ] 2 [(NO) 2 Fe(μ-CO)(μ- S(CH 2 ) 2 NH 3 )Fe(NO) 2 ] (1) → {Fe(NO) 2 } 9 {Fe(NO) 2 } 10 [(NO) 2 Fe(μ-S(CH 2 ) 2 NH 2 )(μ-S(CH 2 ) 2 NH 3 )Fe(NO) 2 ] (2) → RRE 3 is demonstrated. The 1-to-2-to-3 conversion is promoted by proton transfer followed by O 2 oxidation and deprotonation. Additionally, a study on facile conversion of complex 3 to complexes [(SR)(S(CH 2 ) 2 NH 3 )Fe(NO) 2 ] [SR = 2-aminoethanethiolate (4), benzenethiolate (5)] and [(CysS))(S(CH 2 ) 2 NH 3 )Fe(NO) 2 ] (6) via reaction with thiols and the further utility of complex 5 as a template for synthesizing mixed-thiolate-containing reduced RRE (rRRE) [(μ-SC 6 H 5 )(μ-S(CH 2 ) 2 NH 3 )Fe 2 (NO) 4 ] (7) provide the methodology for the synthesis and isolation of neutral, pure cysteine-/mixed-thiolate-containing DNIC/RRE. Compared to the conversion of complex 2 to complex 3 via reaction with O 2 , diphenyl disulfide triggers oxidation of complex 2 to lead to formation of the neutral {Fe(NO) 2 } 9 DNIC 5 and RRE 3. S-S bond activation of diphenyl disulfide by rRRE 2 may support the decay (oxidation) of rRRE species in ToMOC via the reduction of adjacent protein residues such as cystins, proposed by Lippard. © 2013 American Chemical Society.