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Kupper C, Rees JA, Dechert S, et al. Complete Series of {FeNO}(8), {FeNO}(7), and {FeNO}(6) Complexes Stabilized by a Tetracarbene Macrocycle. J Am Chem Soc. 2016;138(25):7888-98doi: 10.1021/jacs.6b00584.
Kupper, C., Rees, J. A., Dechert, S., DeBeer, S., & Meyer, F. (2016). Complete Series of {FeNO}(8), {FeNO}(7), and {FeNO}(6) Complexes Stabilized by a Tetracarbene Macrocycle. Journal of the American Chemical Society, 138(25), 7888-98. https://doi.org/10.1021/jacs.6b00584
Kupper, Claudia, et al. "Complete Series of {FeNO}(8), {FeNO}(7), and {FeNO}(6) Complexes Stabilized by a Tetracarbene Macrocycle." Journal of the American Chemical Society vol. 138,25 (2016): 7888-98. doi: https://doi.org/10.1021/jacs.6b00584
Kupper C, Rees JA, Dechert S, DeBeer S, Meyer F. Complete Series of {FeNO}(8), {FeNO}(7), and {FeNO}(6) Complexes Stabilized by a Tetracarbene Macrocycle. J Am Chem Soc. 2016 Jun 29;138(25):7888-98. doi: 10.1021/jacs.6b00584. Epub 2016 Jun 20. PMID: 27191681.
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J Am Chem Soc. 2016 Jun 29;138(25):7888-98. doi: 10.1021/jacs.6b00584. Epub 2016 Jun 20.

Complete Series of {FeNO}(8), {FeNO}(7), and {FeNO}(6) Complexes Stabilized by a Tetracarbene Macrocycle.

Journal of the American Chemical Society

Claudia Kupper, Julian A Rees, Sebastian Dechert, Serena DeBeer, Franc Meyer

Affiliations

  1. Institut für Anorganische Chemie, Georg-August-Universität , Tammannstrasse 4, D-37077 Göttingen, Germany.
  2. Max Planck Institute for Chemical Energy Conversion , Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
  3. Department of Chemistry, University of Washington , Box 351700, Seattle, Washington 98195-1700, United States.
  4. Department of Chemistry and Biochemistry, Cornell University , Ithaca, New York 14853, United States.

PMID: 27191681 DOI: 10.1021/jacs.6b00584

Abstract

Use of a macrocyclic tetracarbene ligand, which is topologically reminiscent of tetrapyrrole macrocycles though electronically distinct, has allowed for the isolation, X-ray crystallographic characterization and comprehensive spectroscopic investigation of a complete set of {FeNO}(x) complexes (x = 6, 7, 8). Electrochemical reduction, or chemical reduction with CoCp2, of the {FeNO}(7) complex 1 leads to the organometallic {FeNO}(8) species 2. Its crystallographic structure determination is the first for a nonheme iron nitroxyl {FeNO}(8) and has allowed to identify structural trends among the series of {FeNO}(x) complexes. Combined experimental data including (57)Fe Mössbauer, IR, UV-vis-NIR, NMR and Kβ X-ray emission spectroscopies in concert with DFT calculations suggest a largely metal centered reduction of 1 to form the low spin (S = 0) {FeNO}(8) species 2. The very strong σ-donor character of the tetracarbene ligand imparts unusual properties and spectroscopic signatures such as low (57)Fe Mössbauer isomer shifts and linear Fe-N-O units with high IR stretching frequencies for the NO ligand. The observed metal-centered reduction leads to distinct reactivity patterns of the {FeNO}(8) species. In contrast to literature reported {FeNO}(8) complexes, 2 does not undergo NO protonation under strictly anaerobic conditions. Only in the presence of both dioxygen and protons is rapid and clean oxidation to the {FeNO}(7) complex 1 observed. While 1 is stable toward dioxygen, its reaction with dioxygen under NO atmosphere forms the {FeNO}(6)(ONO) complex 3 that features an unusual O-nitrito ligand trans to the NO. 3 is a rare example of a nonheme octahedral {FeNO}(6) complex. Its electrochemical or chemical reduction triggers dissociation of the O-nitrito ligand and sequential formation of the {FeNO}(7) and {FeNO}(8) compounds 1 and 2. A consistent electronic structure picture has been derived for these unique organometallic variants of the key bioinorganic {FeNO}(x) functional units.

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