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  Determination of the g-Tensors and Their Orientations for cis,trans-(L-N2S2)MoVOX (X = Cl, SCH2Ph) by Single-Crystal EPR Spectroscopy and Molecular Orbital Calculations

Mader Cosper, M., Neese, F., Astashkin, A. V., Carducci, M. D., Raitsimring, A. M., & Enemark, J. H. (2005). Determination of the g-Tensors and Their Orientations for cis,trans-(L-N2S2)MoVOX (X = Cl, SCH2Ph) by Single-Crystal EPR Spectroscopy and Molecular Orbital Calculations. Inorganic Chemistry, 44(5), 1290-1301. doi:10.1021/ic0483850.

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 Urheber:
Mader Cosper, Michele1, Autor
Neese, Frank2, Autor           
Astashkin, Andrei V.1, Autor
Carducci, Michael D.1, Autor
Raitsimring, Arnold M.1, Autor
Enemark, John H.1, Autor
Affiliations:
1Department of Chemistry, University of Arizona, Tucson, Arizona 85721-0041, ou_persistent22              
2Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              

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 Zusammenfassung: A single-crystal study of cis,trans-(L-N2S2)MoVOCl (1) doped into cis,trans-(N2S2)MoVIO2 (3) has enabled the g-tensor of 1 and its orientation with respect to the molecular structure to be determined. The EPR parameters (g1, 2.004; g2, 1.960; g3, 1.946; A1, 71.7 × 10-4 cm-1; A2, 11.7 × 10-4 cm-1; A3, 32.0 × 10-4 cm-1) of cis,trans-(L-N2S2)MoVOCl [L-N2S2H2 = N,N‘-dimethyl-N,N‘-bis(mercaptophenyl)ethylenediamine] mimic those of the low-pH form of sulfite oxidase and the “very rapid” species of xanthine oxidase. The principal axis that corresponds to g1 is rotated ∼10° from the Mo⋮O vector, while the principal axis that corresponds to g3 is located in the equatorial plane and ∼38° from the Mo−Cl vector. Independent theoretical calculations of the g-tensor of 1 were performed using two types of techniques:  (1) the spectroscopically parametrized intermediate neglect of differential overlap technique (INDO/S) combined with single-excitation configuration interaction (CIS); (2) a scalar relativistic DFT (BP86 and B3LYP functionals) treatment using the zeroth order regular approximation to relativistic effects (ZORA) in combination with recently developed accurate multicenter mean field spin−orbit operators (RI-SOMF) and the estimation of solvent effects using dielectric continuum theory at the conductor-like screening model (COSMO) level. The excellent agreement between experiment and theory, as well as the high consistency between the INDO/S and BP86/ZORA results, provides a sound basis for analysis of the calculated orientation of the g-tensor for cis,trans-(L-N2S2)MoVO(SCH2Ph) (2), for which single-crystal EPR data are not available but which contains three equatorial sulfur donor atoms, as occurs in sulfite oxidase and xanthine oxidase. The implications of these results for the EPR spectra of the Mo(V) centers of enzymes are discussed.

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Sprache(n): eng - English
 Datum: 2004-11-162005-02-152005-03-01
 Publikationsstatus: Erschienen
 Seiten: 12
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/ic0483850
 Art des Abschluß: -

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Titel: Inorganic Chemistry
  Kurztitel : Inorg. Chem.
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: - Band / Heft: 44 (5) Artikelnummer: - Start- / Endseite: 1290 - 1301 Identifikator: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669