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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 (NO 2 )] 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 1 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 ( 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.

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

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