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  Characterization of a Genuine Iron(V)−Nitrido Species by Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations

Petrenko, T., DeBeer George, S., Aliaga-Alcade, N., Bill, E., Mienert, B., Xiao, Y., et al. (2007). Characterization of a Genuine Iron(V)−Nitrido Species by Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations. Journal of the American Chemical Society, 129(36), 11053-11060. doi:10.1021/ja070792y.

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Petrenko, Taras1, Author
DeBeer George, Serena2, Author
Aliaga-Alcade, Núria3, Author              
Bill, Eckhard4, Author              
Mienert, Bernd4, Author              
Xiao, Yuming5, Author
Guo, YiSong5, Author
Sturhahn, Wolfgang6, Author
Cramer, Stephen P.5, Author
Wieghardt, Karl4, Author              
Neese, Frank1, Author              
Affiliations:
1Lehrstuhl für Theoretische Chemie, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany, ou_persistent22              
2Stanford Synchrotron Radiation Laboratory, SLAC, Stanford University, Stanford, California 94309, ou_persistent22              
3Research Department Lubitz, Max Planck Institute for Radiation Chemistry, Max Planck Society, ou_3023883              
4Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              
5Department of Applied Science, University of California Davis, Davis, California 95616, ou_persistent22              
6Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, ou_persistent22              

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 Abstract: The characterization of high-valent iron species is of interest due to their relevance to biological reaction mechanisms. Recently, we have synthesized and characterized an [Fe(V)-nitrido-cyclam-acetato]+ complex, which has been characterized by Mössbauer, magnetic susceptibility data, and XAS spectroscopies combined with DFT calculations (Aliaga-Alcade, N.; DeBeer George, S.; Bill, E.; Wieghardt, K.; Neese, F. Angew. Chem., Int. Ed.2005, 44, 2908−2912). The results of this study indicated that the [Fe(V)-nitrido-cyclam-acetato]+ complex is an unusual d3 system with a nearly orbitally degenerate S = 1/2 ground state. Although the calculations predicted fairly different Fe−N stretching frequencies for the S = 1/2 and the competing S = 3/2 ground states, a direct experimental determination of this important fingerprint quantity was missing. Here we apply synchrotron-based nuclear resonance vibrational scattering (NRVS) to characterize the Fe−N stretching frequency of an Fe(V)−nitrido complex and its Fe(III)−azide precursor. The NRVS data show a new isolated band at 864 cm-1 in the Fe(V)−nitrido complex that is absent in the precursor. The NRVS spectra are fit and simulated using a DFT approach, and the new feature is unambiguously assigned to a Fe(V)−N stretch. The calculated Fe−N stretching frequency is too high by ∼75 cm-1. Anharmonic contributions to the Fe−N stretching frequency have been evaluated and have been found to be small (−5.5 cm-1). The NRVS data provided a unique opportunity to obtain this vibrational information, which had eluded characterization by more traditional vibrational spectroscopies.

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Language(s): eng - English
 Dates: 2007-02-032007-08-212007-09-01
 Publication Status: Published in print
 Pages: 8
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja070792y
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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: 129 (36) Sequence Number: - Start / End Page: 11053 - 11060 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870