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

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c8sc01962b· OSTI ID:1475536
 [1];  [2];  [3];  [2];  [3];  [3];  [3];  [4];  [5];  [6];  [7];  [6];  [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
+ Show Author Affiliations
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.
Research Organization:
Ewha Womans Univ., Seoul (Korea, Republic of); Johns Hopkins Univ., Baltimore, MD (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
Sponsoring Organization:
National Inst. of Health (NIH) (United States); National Research Foundation of Korea (NRF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1475536
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 34 Vol. 9; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE