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Frantz S, Hartmann H, Doslik N, et al. Multifrequency EPR study and density functional g-tensor calculations of persistent organorhenium radical complexes. J Am Chem Soc. 2002;124(35):10563-71doi: 10.1021/ja025829n.
Frantz, S., Hartmann, H., Doslik, N., Wanner, M., Kaim, W., Kümmerer, H. J., Denninger, G., Barra, A. L., Duboc-Toia, C., Fiedler, J., Ciofini, I., Urban, C., & Kaupp, M. (2002). Multifrequency EPR study and density functional g-tensor calculations of persistent organorhenium radical complexes. Journal of the American Chemical Society, 124(35), 10563-71. https://doi.org/10.1021/ja025829n
Frantz, Stéphanie, et al. "Multifrequency EPR study and density functional g-tensor calculations of persistent organorhenium radical complexes." Journal of the American Chemical Society vol. 124,35 (2002): 10563-71. doi: https://doi.org/10.1021/ja025829n
Frantz S, Hartmann H, Doslik N, Wanner M, Kaim W, Kümmerer HJ, Denninger G, Barra AL, Duboc-Toia C, Fiedler J, Ciofini I, Urban C, Kaupp M. Multifrequency EPR study and density functional g-tensor calculations of persistent organorhenium radical complexes. J Am Chem Soc. 2002 Sep 04;124(35):10563-71. doi: 10.1021/ja025829n. PMID: 12197758.
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J Am Chem Soc. 2002 Sep 04;124(35):10563-71. doi: 10.1021/ja025829n.

Multifrequency EPR study and density functional g-tensor calculations of persistent organorhenium radical complexes.

Journal of the American Chemical Society

Stéphanie Frantz, Heiko Hartmann, Natasa Doslik, Matthias Wanner, Wolfgang Kaim, Hans-Jürgen Kümmerer, Gert Denninger, Anne-Laure Barra, Carole Duboc-Toia, Jan Fiedler, Ilaria Ciofini, Christian Urban, Martin Kaupp

Affiliations

  1. Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany.

PMID: 12197758 DOI: 10.1021/ja025829n

Abstract

The dinuclear radical anion complexes [(mu-L)[Re(CO)(3)Cl](2)](*)(-), L = 2,2'-azobispyridine (abpy) and 2,2'-azobis(5-chloropyrimidine) (abcp), were investigated by EPR at 9.5, 94, 230, and 285 GHz (abpy complex) and at 9.5 and 285 GHz (abcp complex). Whereas the X-band measurements yielded only the isotropic metal hyperfine coupling of the (185,187)Re isotopes, the high-frequency EPR experiments in glassy frozen CH(2)Cl(2)/toluene solution revealed the g components. Both the a((185,187)Re) value and the g anisotropy, g(1) - g(3), are larger for the abcp complex, which contains the better pi-accepting bridging ligand. Confirmation for this comes also from IR and UV/vis spectroscopy of the new [(mu-abcp)[Re(CO)(3)Cl](2)](o/)(*)(-)(/2)(-) redox system. The g values are reproduced reasonably well by density functional calculations which confirm higher metal participation at the singly occupied MO and therefore larger contributions from the metal atoms to the g anisotropy in abcp systems compared to abpy complexes. Additional calculations for a series of systems [(mu-abcp)[M(CO)(3)X](2)](*)(-) (M = Tc or Re and X = Cl, and X = F, Cl, or Br with M = Re) provided further insight into the relationship between spin density distribution and g anisotropy.

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