A mononuclear nonheme {FeNO}⁶ complex: Synthesis and structural and spectroscopic characterization

While the synthesis and characterization of {FeNO}^7,8,9 complexes have been well documented in heme and nonheme iron models, {FeNO}⁶ complexes have been less clearly understood. Herein, we report the synthesis and structural and spectroscopic characterization of mononuclear nonheme {FeNO}⁶ and iron(iii)-nitrito complexes bearing a tetraamido macrocyclic ligand (TAML), such as [(TAML)Fe^III(NO)]^- and [(TAML)Fe^III(NO₂)]^2-, respectively. First, direct addition of NO_(g) to [Fe^III(TAML)]^- results in the formation of [(TAML)Fe^III(NO)]^-, which is sensitive to moisture and air. The spectroscopic data of [(TAML)Fe^III(NO)]^-, such as ¹H nuclear magnetic resonance and X-ray absorption spectroscopies, combined with computational study suggest the neutral nature of nitric oxide with a diamagnetic Fe center (S = 0). We also provide alternative pathways for the generation of [(TAML)Fe^III(NO)]^-, such as the iron-nitrite reduction triggered by protonation in the presence of ferrocene, which acts as an electron donor, and the photochemical iron-nitrite reduction. To the best of our knowledge, the present study reports the first photochemical nitrite reduction in nonheme iron models.