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Russian Chemical Bulletin

, Volume 47, Issue 5, pp 868–874 | Cite as

Structures of Rydberg transitions in the absorption spectra of methyl-substituted derivatives of bis(η6-benzene)chromium

  • S. Yu. Ketkov
  • G. A. Domrachev
  • C. P. Mehnert
  • J. C. Green
Physical Chemistry

Abstract

The effect of methylation of ligands in bis(η6-benzene)chromium (1) on the structure of Rydberg transitions in absorption spectra has been studied. A detailed analysis and interpretation of all Rydberg elements of the vapor-phase spectra of bis(η6-benzene)chromium (2), bis(η6-o-xylene)chromium (3), bis(η6-m-xylene)chromium (4), and bis(η6-mesitylene)chromium (5) was carried out. The vapor-phase electronic absorption spectrum of bis(η6-p-xylene)chromium (6) was measured, and the assignment of the Rydberg bands was made for the first time. The first ionization potentials of complexes 2–5 were refined. The energy of detachment of the 3dz 2 electron and the parameters of the Rydberg excitations for molecule 6 were determined. The vibronic components of the 3dz 2R4p x,y transition in the spectra of complexes 2 and 6 were assigned. The differences in the Rydberg structure of the spectra of compounds 2–6 were analyzed in terms of the selection rules for optical transitions in the corresponding symmetry groups. The vapor-phase spectra correspond to conformers with the symmetry groupsC 2v andC 2 for complexes 2–4, with the symmetry groupsD 3h andD 3 for compound 5, and with the symmetry groupD 2d for complex 6.

Key words

bisarenechromium complexes, methyl-substituted derivatives of bis(η6-benzene)chromium, molecular symmetry electronic absorption spectra, Rydberg transitions 

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Copyright information

© Plenum Publishing Corporation 1998

Authors and Affiliations

  • S. Yu. Ketkov
    • 1
  • G. A. Domrachev
    • 1
  • C. P. Mehnert
    • 2
  • J. C. Green
    • 2
  1. 1.A. Razuvaev Institute of Organometallic ChemistryRussian Academy of SciencesNizhnii NovgorodRussian Federation
  2. 2.Inorganic Chemistry LaboratoryUniversity of OxfordOxfordUK

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