While the synthesis and characterization of {FeNO} complexes have been well documented in heme and nonheme iron models, {FeNO} complexes have been less clearly understood. Herein, we report the synthesis and structural and spectroscopic characterization of mononuclear nonheme {FeNO} and iron(iii)-nitrito complexes bearing a tetraamido macrocyclic ligand (TAML), such as [(TAML)Fe(NO)] and [(TAML)Fe(NO)], respectively. First, direct addition of NO to [Fe(TAML)] results in the formation of [(TAML)Fe(NO)], which is sensitive to moisture and air. The spectroscopic data of [(TAML)Fe(NO)], such as H nuclear magnetic resonance and X-ray absorption spectroscopies, combined with computational study suggest the neutral nature of nitric oxide with a diamagnetic Fe center ( = 0). We also provide alternative pathways for the generation of [(TAML)Fe(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.
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