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Title: 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(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 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.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ;  [3] ;  [2] ;  [3] ; ORCiD logo [3] ;  [3] ; ORCiD logo [4] ;  [5] ;  [6] ; ORCiD logo [7] ; ORCiD logo [6] ; ORCiD logo [8]
  1. Ewha Womans Univ., Seoul (Korea, Republic of). Dept. of Chemistry and Nano Science; Sookmyung Women's Univ., Seoul (Korea, Republic of). Dept. of Chemistry
  2. Stanford Univ., CA (United States). Dept. of Chemistry
  3. Ewha Womans Univ., Seoul (Korea, Republic of). Dept. of Chemistry and Nano Science
  4. Univ. of California, Santa Cruz, CA (United States). Dept. of Chemistry and Biochemistry
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
  6. Stanford Univ., CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
  7. Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry
  8. Ewha Womans Univ., Seoul (Korea, Republic of). Dept. of Chemistry and Nano Science; Shaanxi Normal Univ., Xi'an (China). School of Chemistry and Chemical Engineering
Publication Date:
Grant/Contract Number:
AC02-76SF00515; GM-28962; GM-40392; P41GM103393; NRF-2012R1A3A2048842; NRF-2010-00353; NRF-2017R1C1B2002037
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 34; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States); Johns Hopkins Univ., Baltimore, MD (United States); Ewha Womans Univ., Seoul (Korea, Republic of)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Inst. of Health (NIH) (United States); National Research Foundation of Korea (NRF)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1475536

Hong, Seungwoo, Yan, James J., Karmalkar, Deepika G., Sutherlin, Kyle D., Kim, Jin, Lee, Yong-Min, Goo, Yire, Mascharak, Pradip K., Hedman, Britt, Hodgson, Keith O., Karlin, Kenneth D., Solomon, Edward I., and Nam, Wonwoo. A mononuclear nonheme {FeNO}6 complex: synthesis and structural and spectroscopic characterization. United States: N. p., Web. doi:10.1039/c8sc01962b.
Hong, Seungwoo, Yan, James J., Karmalkar, Deepika G., Sutherlin, Kyle D., Kim, Jin, Lee, Yong-Min, Goo, Yire, Mascharak, Pradip K., Hedman, Britt, Hodgson, Keith O., Karlin, Kenneth D., Solomon, Edward I., & Nam, Wonwoo. A mononuclear nonheme {FeNO}6 complex: synthesis and structural and spectroscopic characterization. United States. doi:10.1039/c8sc01962b.
Hong, Seungwoo, Yan, James J., Karmalkar, Deepika G., Sutherlin, Kyle D., Kim, Jin, Lee, Yong-Min, Goo, Yire, Mascharak, Pradip K., Hedman, Britt, Hodgson, Keith O., Karlin, Kenneth D., Solomon, Edward I., and Nam, Wonwoo. 2018. "A mononuclear nonheme {FeNO}6 complex: synthesis and structural and spectroscopic characterization". United States. doi:10.1039/c8sc01962b. https://www.osti.gov/servlets/purl/1475536.
@article{osti_1475536,
title = {A mononuclear nonheme {FeNO}6 complex: synthesis and structural and spectroscopic characterization},
author = {Hong, Seungwoo and Yan, James J. and Karmalkar, Deepika G. and Sutherlin, Kyle D. and Kim, Jin and Lee, Yong-Min and Goo, Yire and Mascharak, Pradip K. and Hedman, Britt and Hodgson, Keith O. and Karlin, Kenneth D. and Solomon, Edward I. and Nam, Wonwoo},
abstractNote = {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.},
doi = {10.1039/c8sc01962b},
journal = {Chemical Science},
number = 34,
volume = 9,
place = {United States},
year = {2018},
month = {7}
}

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