Structures of Rydberg transitions in the absorption spectra of methyl-substituted derivatives of bis(η6-benzene)chromium |
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Authors: | S. Yu. Ketkov G. A. Domrachev C. P. Mehnert J. C. Green |
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Affiliation: | (1) A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603600 Nizhnii Novgorod, Russian Federation;(2) Inorganic Chemistry Laboratory, University of Oxford, OX1 3QR Oxford, UK |
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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 2→R4p 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. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 897–903, May, 1998. |
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Keywords: | bisarenechromium complexes, methyl-substituted derivatives of bis(η 6-benzene)chromium, molecular symmetry electronic absorption spectra, Rydberg transitions |
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