skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Stable Ferrous Mononitroxyl {FeNO}8 Complex with a Hindered Hydrotris(pyrazolyl)borate Coligand: Structure, Spectroscopic Characterization, and Reactivity Toward NO and O2

Journal Article · · Inorganic Chemistry
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)
+ Show Author Affiliations

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
Japan Society for the Promotion of Science (JSPS); National Science Foundation (NSF); USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1515860
Journal Information:
Inorganic Chemistry, Vol. 58, Issue 7; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

References (22)

Recent advances in multinuclear metal nitrosyl complexes journal January 2016
Principles of structure, bonding, and reactivity for metal nitrosyl complexes journal September 1974
Flavo-diiron enzymes: nitric oxide or dioxygen reductases? journal January 2007
Structural Basis of Biological N2O Generation by Bacterial Nitric Oxide Reductase journal November 2010
Electronic Structure and FeNO Conformation of Nonheme Iron−Thiolate−NO Complexes:  An Experimental and DFT Study journal August 2007
The Functional Model Complex [Fe 2 (BPMP)(OPr)(NO) 2 ](BPh 4 ) 2 Provides Insight into the Mechanism of Flavodiiron NO Reductases journal March 2013
Unusual Synthetic Pathway for an {Fe(NO) 2 } 9 Dinitrosyl Iron Complex (DNIC) and Insight into DNIC Electronic Structure via Nuclear Resonance Vibrational Spectroscopy journal May 2016
Reductive Transformations of a Pyrazolate-Based Bioinspired Diiron–Dinitrosyl Complex journal October 2016
Structural, Spectroscopic, and Computational Study of an Octahedral, Non-Heme {Fe−NO}6-8 Series:  [Fe(NO)(cyclam-ac)]2+/+/0 journal April 2004
A thermally stable {FeNO} 8 complex: properties and biological reactivity of reduced MNO systems journal January 2012
Complete Series of {FeNO} 8 , {FeNO} 7 , and {FeNO} 6 Complexes Stabilized by a Tetracarbene Macrocycle journal June 2016
A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO} 8-10 journal August 2016
A Nonheme, High-Spin {FeNO} 8 Complex that Spontaneously Generates N 2 O journal July 2017
Non-heme High-Spin {FeNO} 6–8 Complexes: One Ligand Platform Can Do It All journal August 2018
63 Cu NMR Study of Copper(I) Carbonyl Complexes with Various Hydrotris(pyrazolyl)borates:  Correlation between 63 Cu Chemical Shifts and CO Stretching Vibrations journal June 1998
Solid-state structures of dinitrosyliron iodide and dinitrosylcobalt iodide: stereochemical consequences of strong metal-metal interactions in ligand-bridged complexes journal March 1969
Structural and Spectroscopic Characterization of First-Row Transition Metal(II) Substituted Blue Copper Model Complexes with Hydrotris(pyrazolyl)borate journal January 2005
Spectroscopic and DFT Investigation of [M{HB(3,5- i Pr 2 pz) 3 }(SC 6 F 5 )] (M = Mn, Fe, Co, Ni, Cu, and Zn) Model Complexes:  Periodic Trends in Metal−Thiolate Bonding journal July 2005
Magnetic Circular Dichroism Spectroscopic Studies of Mononuclear Non-Heme Ferrous Model Complexes. Correlation of Excited- and Ground-State Electronic Structure with Geometry journal April 1998
Structural and Electronic Characterization of Non-Heme Fe(II)–Nitrosyls as Biomimetic Models of the Fe B Center of Bacterial Nitric Oxide Reductase journal October 2011
A cobalt–nitrosyl complex with a hindered hydrotris(pyrazolyl)borate coligand: detailed electronic structure, and reactivity towards dioxygen journal January 2017
Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure journal June 2016

Cited By (1)

Structures and Properties of Dinitrosyl Iron and Cobalt Complexes Ligated by Bis(3,5-diisopropyl-1-pyrazolyl)methane journal September 2019

Linked Research (3)

Similar Records

Unusual Synthetic Pathway for an {Fe(NO)2}9 Dinitrosyl Iron Complex (DNIC) and Insight into DNIC Electronic Structure via Nuclear Resonance Vibrational Spectroscopy
Journal Article · Mon Jun 06 00:00:00 EDT 2016 · Inorganic Chemistry · OSTI ID:1515860
+7 more
Non-heme High-Spin {FeNO}6–8 Complexes: One Ligand Platform Can Do It All
Journal Article · Tue Aug 14 00:00:00 EDT 2018 · Journal of the American Chemical Society · OSTI ID:1515860
+6 more
Thermally stable manganese(Ⅲ) peroxido complexes with hindered N3 tripodal ligands: Structures and their physicochemical properties
Journal Article · Thu Sep 02 00:00:00 EDT 2021 · Journal of Inorganic Biochemistry · OSTI ID:1515860
+2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY