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  Structural, Spectroscopic, and Computational Study of an Octahedral, Non-Heme {Fe−NO}6-8 Series:  [Fe(NO)(cyclam-ac)]2+/+/0

García Serres, R., Grapperhaus, C. A., Bothe, E., Bill, E., Weyhermüller, T., Neese, F., et al. (2004). Structural, Spectroscopic, and Computational Study of an Octahedral, Non-Heme {Fe−NO}6-8 Series:  [Fe(NO)(cyclam-ac)]2+/+/0. Journal of the American Chemical Society, 126(16), 5138-5153. doi:10.1021/ja030645+.

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 Creators:
García Serres, Ricardo1, Author              
Grapperhaus, Craig A.1, Author              
Bothe, Eberhard1, Author              
Bill, Eckhard1, Author              
Weyhermüller, Thomas1, Author              
Neese, Frank1, Author              
Wieghardt, Karl1, Author              
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1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              

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 Abstract: The reaction of low-spin [FeIICl(cyclam-ac)] with NO in CH3CN yields the octahedral, non-heme (nitrosyl)iron complex [Fe(NO)(cyclam-ac)](PF6) (2), S = 1/2, which can be one-electron oxidized with (tris(4-bromophenyl)ammoniumyl)hexachloroantimonate to the complex [Fe(NO)(cyclam-ac)](PF6)2 (1‘), S = 0, or complex [Fe(NO)(cyclam-ac)]Cl(ClO4)·H2O (1); (cyclam-ac)- represents the pentadentate monoanion of 1,4,8,11-tetraazacyclotetradecane-1-acetic acid. Similarly, in CH3CN solution 2 can be electrochemically or chemically reduced by one-electron to the neutral complex [Fe(NO)(cyclam-ac)]0 (3), S = 0. 1−3 represent members of the {FeNO}6-8 series, respectively. The electronic structure of these three species have been spectroscopically elucidated by EPR, UV−vis, Mössbauer, and IR spectroscopy. The crystal structures of 1 and 2 have been determined by X-ray crystallography. In addition, detailed density functional calculations have been performed for all three species taking into account the possibility that 3 is actually a protonated HNO or NOH species. For all complexes structures, energetics, IR parameters, and Mössbauer parameters as well as EPR parameters (g-values and hyperfine couplings) have been calculated using state-of-the art DFT methods which are compared to experiment. The results establish unequivocally that 3 is indeed the elusive {FeNO}8 species. Furthermore a detailed picture of the bonding in the low-spin non-heme iron nitrosyl series {FeNO}6, {FeNO}7, and {FeNO}8 has been developed. This allows a description of 1 as a low-spin ferrous complex containing an N-coordinated NO+, whereas 2 is a low-spin ferrous species with a NO ligand and 3 is a low-spin ferrous complex with a coordinated NO-. On the basis of this description, all spectroscopic and geometric observables find a satisfactory interpretation.

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Language(s): eng - English
 Dates: 2003-12-032004-04-062004-04-28
 Publication Status: Published in print
 Pages: 16
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja030645+
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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 126 (16) Sequence Number: - Start / End Page: 5138 - 5153 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870