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Title: Stable Ferrous Mononitroxyl {FeNO} 8 Complex with a Hindered Hydrotris(pyrazolyl)borate Coligand: Structure, Spectroscopic Characterization, and Reactivity Toward NO and O 2

Abstract

The iron(II)-nitroxyl complex [Fe(NO)(L3)] (1) (with L3 = a hindered hydrotris(pyrazolyl)borate ligand), a high-spin (hs)-{FeNO} 8 complex in the Enemark–Feltham notation, is surprisingly stable and is the first of its kind that could be structurally characterized. We further studied this compound using a variety of spectroscopic methods. These results indicate a hs iron(II) center with a bound 3NO ligand where the spins are antiferromagnetic coupled ( S t = 1). Vibrational data show that this complex has a very strong Fe–NO bond. DFT calculations support this result and link it to very strong π-donation from the 3NO ligand to the iron(II) center. Furthermore, a very unusual equilibrium between the hs-{FeNO} 8 complex and a dinitrosyl iron complex (DNIC) of {Fe(NO) 2} 9 type is observed. In conclusion, the O 2 reactivity of the complex is finally reported.

Authors:
ORCiD logo [1];  [2];  [1];  [1]; ORCiD logo [3];  [1];  [4];  [4];  [4]; ORCiD logo [3]
  1. Ibaraki Univ., Mito (Japan)
  2. Ibaraki Univ., Mito (Japan); Univ. of Michigan, Ann Arbor, MI (United States)
  3. Univ. of Michigan, Ann Arbor, MI (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Japan Society for the Promotion of Science (JSPS); National Science Foundation (NSF); USDOE
OSTI Identifier:
1515860
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 7; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Fujisawa, Kiyoshi, Soma, Shoko, Kurihara, Haruka, Ohta, Ayuri, Dong, Hai T., Minakawa, Yurika, Zhao, Jiyong, Alp, E. Ercan, Hu, Michael Y., and Lehnert, Nicolai. Stable Ferrous Mononitroxyl {FeNO}8 Complex with a Hindered Hydrotris(pyrazolyl)borate Coligand: Structure, Spectroscopic Characterization, and Reactivity Toward NO and O2. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.9b00107.
Fujisawa, Kiyoshi, Soma, Shoko, Kurihara, Haruka, Ohta, Ayuri, Dong, Hai T., Minakawa, Yurika, Zhao, Jiyong, Alp, E. Ercan, Hu, Michael Y., & Lehnert, Nicolai. Stable Ferrous Mononitroxyl {FeNO}8 Complex with a Hindered Hydrotris(pyrazolyl)borate Coligand: Structure, Spectroscopic Characterization, and Reactivity Toward NO and O2. United States. https://doi.org/10.1021/acs.inorgchem.9b00107
Fujisawa, Kiyoshi, Soma, Shoko, Kurihara, Haruka, Ohta, Ayuri, Dong, Hai T., Minakawa, Yurika, Zhao, Jiyong, Alp, E. Ercan, Hu, Michael Y., and Lehnert, Nicolai. Wed . "Stable Ferrous Mononitroxyl {FeNO}8 Complex with a Hindered Hydrotris(pyrazolyl)borate Coligand: Structure, Spectroscopic Characterization, and Reactivity Toward NO and O2". United States. https://doi.org/10.1021/acs.inorgchem.9b00107. https://www.osti.gov/servlets/purl/1515860.
@article{osti_1515860,
title = {Stable Ferrous Mononitroxyl {FeNO}8 Complex with a Hindered Hydrotris(pyrazolyl)borate Coligand: Structure, Spectroscopic Characterization, and Reactivity Toward NO and O2},
author = {Fujisawa, Kiyoshi and Soma, Shoko and Kurihara, Haruka and Ohta, Ayuri and Dong, Hai T. and Minakawa, Yurika and Zhao, Jiyong and Alp, E. Ercan and Hu, Michael Y. and Lehnert, Nicolai},
abstractNote = {The iron(II)-nitroxyl complex [Fe(NO)(L3)] (1) (with L3– = a hindered hydrotris(pyrazolyl)borate ligand), a high-spin (hs)-{FeNO}8 complex in the Enemark–Feltham notation, is surprisingly stable and is the first of its kind that could be structurally characterized. We further studied this compound using a variety of spectroscopic methods. These results indicate a hs iron(II) center with a bound 3NO– ligand where the spins are antiferromagnetic coupled (St = 1). Vibrational data show that this complex has a very strong Fe–NO bond. DFT calculations support this result and link it to very strong π-donation from the 3NO– ligand to the iron(II) center. Furthermore, a very unusual equilibrium between the hs-{FeNO}8 complex and a dinitrosyl iron complex (DNIC) of {Fe(NO)2}9 type is observed. In conclusion, the O2 reactivity of the complex is finally reported.},
doi = {10.1021/acs.inorgchem.9b00107},
url = {https://www.osti.gov/biblio/1515860}, journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 7,
volume = 58,
place = {United States},
year = {2019},
month = {3}
}

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Works referencing / citing this record:

CCDC 1866552: Experimental Crystal Structure Determination
dataset, January 2019


CCDC 1866553: Experimental Crystal Structure Determination
dataset, January 2019


CCDC 1866554: Experimental Crystal Structure Determination
dataset, January 2019