5864-44-8Relevant articles and documents
Insight into one-electron oxidation of the {Fe(NO)2}9 dinitrosyl iron complex (DNIC): Aminyl radical stabilized by [Fe(NO) 2] motif
Tsou, Chih-Chin,Tsai, Fu-Te,Chen, Huang-Yeh,Hsu, I-Jui,Liaw, Wen-Feng
, p. 1631 - 1639 (2013)
A reversible redox reaction ({Fe(NO)2}9 DNIC [(NO)2Fe(N(Mes)(TMS))2]- (4) ? oxidized-form DNIC [(NO)2Fe(N(Mes)(TMS))2] (5) (Mes = mesityl, TMS = trimethylsilane)), characterized by IR, UV-vis, 1H/15N NMR, SQUID, XAS, single-crystal X-ray structure, and DFT calculation, was demonstrated. The electronic structure of the oxidized-form DNIC 5 (Stotal = 0) may be best described as the delocalized aminyl radical [(N(Mes)(TMS))2]2 -? stabilized by the electron-deficient {Fe III(NO-)2}9 motif, that is, substantial spin is delocalized onto the [(N(Mes)(TMS))2] 2-? such that the highly covalent dinitrosyl iron core (DNIC) is preserved. In addition to IR, EPR (g ≈ 2.03 for {Fe(NO) 2}9), single-crystal X-ray structure (Fe-N(O) and N-O bond distances), and Fe K-edge pre-edge energy (7113.1-7113.3 eV for {Fe(NO) 2}10 vs 7113.4-7113.9 eV for {Fe(NO)2} 9), the 15N NMR spectrum of [Fe(15NO) 2] was also explored to serve as an efficient tool to characterize and discriminate {Fe(NO)2}9 (δ 23.1-76.1 ppm) and {Fe(NO)2}10 (δ -7.8-25.0 ppm) DNICs. To the best of our knowledge, DNIC 5 is the first structurally characterized tetrahedral DNIC formulated as covalent-delocalized [{FeIII(NO-) 2}9-[N(Mes)(TMS)]2-?]. This result may explain why all tetrahedral DNICs containing monodentate-coordinate ligands isolated and characterized nowadays are confined in the {Fe(NO) 2}9 and {Fe(NO)2}10 DNICs in chemistry and biology.