Issue 34, 2018

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

Abstract

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)FeIII(NO)] and [(TAML)FeIII(NO2)]2−, respectively. First, direct addition of NO(g) to [FeIII(TAML)] results in the formation of [(TAML)FeIII(NO)], which is sensitive to moisture and air. The spectroscopic data of [(TAML)FeIII(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)FeIII(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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
01 May 2018
Accepted
18 Jul 2018
First published
20 Jul 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 6952-6960

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

S. Hong, J. J. Yan, D. G. Karmalkar, K. D. Sutherlin, J. Kim, Y. Lee, Y. Goo, P. K. Mascharak, B. Hedman, K. O. Hodgson, K. D. Karlin, E. I. Solomon and W. Nam, Chem. Sci., 2018, 9, 6952 DOI: 10.1039/C8SC01962B

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