Characterization of a Genuine lron(V)-Nitrido Species by Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations.
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 spectr...
| Publicado en: | Journal of the American Chemical Society Vol. 129; no. 36; pp. 1053 - 1061 |
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| Autores principales: | , , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
9/12/2007
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=26760278&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 26760278 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 9/12/2007 vid: 129 iid: 36 pid: 997 pub: American Chemical Society artinfo: ui: 26760278 10.1021/ja070792y ppf: 1053 ppct: 8 formats: tig: atl: Characterization of a Genuine lron(V)-Nitrido Species by Nuclear Resonant Vibrational Spectroscopy Coupled to Density Functional Calculations. aug: au: Petrenko, Taras Debeer George, Serena Aliaga-Alcalde, Nüria Bill, Eckhard Mienert, Bernd Yuming Xiao YiSong Guo Sturhahn, Wolfgang Cramer, Stephen P. Wieghardt, Karl Neese, Frank affil: Institut für Physikalische und Theoretische Cheniie, Wegelerstr. 12, D-53 I/S Bonn, Germany Stanford Synchrotron Radiation Laboratory, SL4C, Stanford University, Stanford, California 94309 Max-Planck institut für Bioanorganische Chemie, Stiftstr. 34-36; D-45470 Miilheim an der Ruhr, Germany Department of Applied Science, University of California Davis, Davis, California 95616 Advanced Photon Source, Argonne National Laboratory, Argonne, illinois 60439 Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 su: Iron Vibrational spectra Density functionals Organic synthesis Transition metal complexes sug: subj: Iron Vibrational spectra Density functionals Organic synthesis Transition metal complexes ab: 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 = 1/2 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 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. Anharmonic contributions to the Fe-N stretching frequency have been evaluated and have been found to be small (-5.5 cm). The NRVS data provided a unique opportunity to obtain this vibrational information, which had eluded characterization by more traditional vibrational spectroscopies. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2007 holdings: @attributes: islocal: N |
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