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  Magnetic circular dichroism and computational study of mononuclear and dinuclear iron(IV) complexes

Ye, S., Xue, G., Krivokapic, I., Petrenko, T., Bill, E., Que, Jr., L., et al. (2015). Magnetic circular dichroism and computational study of mononuclear and dinuclear iron(IV) complexes. Chemical Science, 6(5), 2909-2921. doi:10.1039/C4SC03268C.

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 Creators:
Ye, Shengfa1, Author              
Xue, Genqiang2, Author
Krivokapic, Itana1, Author              
Petrenko, Taras1, Author              
Bill, Eckhard1, Author              
Que, Jr., Lawrence2, Author
Neese, Frank1, Author              
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Department of Chemistry, Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, USA, ou_persistent22              

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 Abstract: High-valent iron(IV)-oxo species are key intermediates in the catalytic cycles of a range of O2-activating iron enzymes. This work presents a detailed study of the electronic structures of mononuclear ([FeIV(O)(L)(NCMe)]2+, 1, L = tris(3,5-dimethyl-4-methoxylpyridyl-2-methyl)amine) and dinuclear ([(L)FeIV(O)(μ-O)FeIV(OH)(L)]3+, 2) iron(IV) complexes using absorption (ABS), magnetic circular dichroism (MCD) spectroscopy and wave-function-based quantum chemical calculations. For complex 1, the experimental MCD spectra at 2–10 K are dominated by a broad positive band between 12 000 and 18 000 cm−1. As the temperature increases up to ∼20 K, this feature is gradually replaced by a derivative-shaped signal. The computed MCD spectra are in excellent agreement with experiment, which reproduce not only the excitation energies and the MCD signs of key transitions but also their temperature-dependent intensity variations. To further corroborate the assignments suggested by the calculations, the individual MCD sign for each transition is independently determined from the corresponding electron donating and accepting orbitals. Thus, unambiguous assignments can be made for the observed transitions in 1. The ABS/MCD data of complex 2 exhibit ten features that are assigned as ligand-field transitions or oxo- or hydroxo-to-metal charge transfer bands, based on MCD/ABS intensity ratios, calculated excitation energies, polarizations, and MCD signs. In comparison with complex 1, the electronic structure of the FeIV=O site is not significantly perturbed by the binding to another iron(IV) center. This may explain the experimental finding that complexes 1 and 2 have similar reactivities toward C–H bond activation and O-atom transfer.

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Language(s): eng - English
 Dates: 2014-10-242015-02-262015-05-01
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C4SC03268C
 Degree: -

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Title: Chemical Science
  Abbreviation : Chem. Sci.
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: 6 (5) Sequence Number: - Start / End Page: 2909 - 2921 Identifier: ISSN: 2041-6520
CoNE: https://pure.mpg.de/cone/journals/resource/2041-6520