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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

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García Serres,  Ricardo
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Grapperhaus,  Craig A.
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Bothe,  Eberhard
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Bill,  Eckhard
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Weyhermüller,  Thomas
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Neese,  Frank
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Wieghardt,  Karl
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Citation

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+.


Cite as: http://hdl.handle.net/21.11116/0000-0008-1080-4
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.