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

Seungwoo Hong, James J. Yan, Deepika G. Karmalkar, Kyle D. Sutherlin, Jin Kim, Yong Min Lee, Yire Goo, Pradip K. Mascharak, Britt Hedman, Keith O. Hodgson, Kenneth D. Karlin, Edward I. Solomon, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


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.

Original languageEnglish
Pages (from-to)6952-6960
Number of pages9
JournalChemical Science
Issue number34
StatePublished - 2018

Bibliographical note

Funding Information:
This work was supported by NRF of Korea through CRI (NRF-2012R1A3A2048842 to W. N.), GRL (NRF-2010-00353 to W. N.), MSIP (NRF-2017R1C1B2002037 to S. H.) and the USA National Institutes of Health (GM-28962 to K. D. K. and GM-40392 to E. I. S.). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research, and by the National Institutes of Health, National Institute of General Medical Sciences (P41GM103393 to K. O. H and B. H.).

Publisher Copyright:
© 2018 The Royal Society of Chemistry.


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