CHIEN-HONG CHEN2026-10-162026-10-162005-09-19Pure ID: 14966370Pure UUID: 6fdf92dc-b83b-4846-a8ee-de0ddfa4c71110.1021/ic050108lhttps://www.scopus.com/pages/publications/25444468542https://scholars.csmu.edu.tw/handle/123456789/30306The five-coordinated iron-thiolate nitrosyl complexes [(NO)Fe(S,-C 6H3R)2]- (R = H (1), m-CH 3 (2)), [(NO)Fe-(S,S-C6H2-3,6-Cl 2)2]- (3), [(NO)Fe(S,S-C6H 3R)2]2- (R = H (10), m-CH3 (11)), and [(NO)Fe(S,S-C6H2-3,6-Cl2)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 O2 to yield the S-bonded monosulfinate iron species [(NO)Fe-(S,SO2-C6H 3R)(S,S-C6H3R)]- (R = H (4), m-CH3 (5)) and [(NO)Fe(S,SO2-C6H 2-3,6-Cl2)(S,S-C6H2-3,6-Cl 2)]22- (6), respectively. In contrast, attack of O2 on the {Fe(NO)}7 complex 10 led to the formation of complex 1 accompanied by the minor products, [Fe(S,S-C6H 4)2]22- and [NO3] - (yield 9%). Reduction of complexes 4-6 by [EtS]- in CH3-CN-THF yielded [(NO)Fe(S,SO2-C6H 3R)(S,S-C6H3R)]2- (R = H (7), m-CH3 (8)) and [(NO)Fe(S,SO2-C6H 2-3,6-Cl2)-(S,S-C6H2-3,6-Cl 2)]2- (9) along with (EtS)2 identified by 1H 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 O2 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 O2. 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.10enjournal article