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Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]-: formation pathway of dinitrosyl iron complexes (DNICs) from nitrosylation of biomimetic rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et)
Authors:Lu Tsai-Te  Chiou Show-Jen  Chen Chun-Yu  Liaw Wen-Feng
Institution:Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
Abstract:Nitrosylation of the biomimetic reduced- and oxidized-form rubredoxin Fe(SR)4]2-/1- (R = Ph, Et) in a 1:1 stoichiometry led to the formation of the extremely air- and light-sensitive mononitrosyl tris(thiolate) iron complexes (MNICs) Fe(NO)(SR)3]- along with byproducts SR]- or (RS)2. Transformation of Fe(NO)(SR)3]- into dinitrosyl iron complexes (DNICs) (RS)2Fe(NO)2]- and Roussin's red ester Fe2(mu-SR)2(NO)4] occurs rapidly under addition of 1 equiv of NO(g) and NO]+, respectively. Obviously, the mononitrosyl tris(thiolate) complex Fe(NO)(SR)3]- acts as an intermediate when the biomimetic oxidized- and reduced-form rubredoxin Fe(SR)4]2-/1- exposed to NO(g) were modified to form dinitrosyl iron complexes (RS)2Fe(NO)2]-. Presumably, NO binding to the electron-deficient Fe(III)(SR)4]- and Fe(III)(NO)(SR)3]- complexes triggers reductive elimination of dialkyl/diphenyl disulfide, while binding of NO radical to the reduced-form Fe(II)(SR)4]2- induces the thiolate-ligand elimination. Protonation of Fe(NO)(SEt)3]- yielding Fe(NO)(SPh)3]- by adding 3 equiv of thiophenol and transformation of Fe(NO)(SPh)3]- to Fe(NO)(SEt)3]- in the presence of 3 equiv of SEt]-, respectively, demonstrated that complexes Fe(NO)(SPh)3]- and Fe(NO)(SEt)3]- are chemically interconvertible. Mononitrosyl tris(thiolate) iron complex Fe(NO)(SPh)3]- and dinitrosyl iron complex (EtS)2Fe(NO)2]- were isolated and characterized by X-ray diffraction. The mean NO bond distances of 1.181(7) A (or 1.191(7) A) in complex (EtS)2Fe(NO)2]- are nearly at the upper end of the 1.178(3)-1.160(6) A for the anionic {Fe(NO)2}9 DNICs, while the mean FeN(O) distances of 1.674(6) A (or 1.679(6) A) exactly fall in the range of 1.695(3)-1.661(4) A for the anionic {Fe(NO)2}9 DNICs.
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