摘要
The five-coordinated iron-thiolate nitrosyl complexes [(NO)Fe(S,-C 6 H 3 R) 2 ] - (R = H (1), m-CH 3 (2)), [(NO)Fe-(S,S-C 6 H 2 -3,6-Cl 2 ) 2 ] - (3), [(NO)Fe(S,S-C 6 H 3 R) 2 ] 2- (R = H (10), m-CH 3 (11)), and [(NO)Fe(S,S-C 6 H 2 -3,6-Cl 2 ) 2 ] 2- (12) have been isolated and structurally characterized. Sulfur oxygenation of iron-thiolate nitrosyl complexes 1-3 containing the {Fe(NO)} 6 core was triggered by O 2 to yield the S-bonded monosulfinate iron species [(NO)Fe-(S,SO 2 -C 6 H 3 R)(S,S-C 6 H 3 R)] - (R = H (4), m-CH 3 (5)) and [(NO)Fe(S,SO 2 -C 6 H 2 -3,6-Cl 2 )(S,S-C 6 H 2 -3,6-Cl 2 )] 2 2- (6), respectively. In contrast, attack of O 2 on the {Fe(NO)} 7 complex 10 led to the formation of complex 1 accompanied by the minor products, [Fe(S,S-C 6 H 4 ) 2 ] 2 2- and [NO 3 ] - (yield 9%). Reduction of complexes 4-6 by [EtS] - in CH 3 -CN-THF yielded [(NO)Fe(S,SO 2 -C 6 H 3 R)(S,S-C 6 H 3 R)] 2- (R = H (7), m-CH 3 (8)) and [(NO)Fe(S,SO 2 -C 6 H 2 -3,6-Cl 2 )-(S,S-C 6 H 2 -3,6-Cl 2 )] 2- (9) along with (EtS) 2 identified by 1 H NMR. Compared to complex 10, complexes 7-9 with the less electron-donating sulfinate ligand coordinated to the {Fe(NO)} 7 core were oxidized by O 2 to yield complexes 4-6. Obviously, the electronic perturbation of the {Fe(NO)} 7 core caused by the coordinated sulfinate in complexes 7-9 may serve to regulate the reactivity of complexes 7-9 toward O 2 . The iron-sulfinate nitrosyl species with the {Fe(NO)} 6/7 core exhibit the photolabilization of sulfur-bound [O] moiety. Complexes 1-4-7-10 (or 2-5-8-11 and 3-6-9-12) are interconvertible under sulfur oxygenation, redox processes, and photolysis, respectively. © 2005 American Chemical Society.