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Spectral and bonding properties of new o‐, m‐, and p‐hydroxydithiobenzoate complexes of some trivalent open‐shell central atoms studied by experimental and HMO quantum‐chemical methods
Author(s) -
Tsipis C. A.,
Sigalas M. P.,
Hadjikostas C. C.
Publication year - 1983
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19835051007
Subject(s) - ligand field theory , chemistry , ligand (biochemistry) , spectrochemical series , spectral line , electronic structure , open shell , chemical bond , crystallography , computational chemistry , ion , physics , organic chemistry , biochemistry , receptor , astronomy
Abstract New complexes of Cr(III), Fe(III) and Co(III) with the o‐, m‐ and p‐hydroxydithiobenzoato ligands have been prepared and characterized. The bonding properties in these complexes are discussed in the light of HMO quantum‐chemical calculations. By estimation of the effect of metal‐ligand π‐bonding on the electronic transition energies in the case of the p‐hydroxydithiobenzoate complexes their electronic transitions have been fully characterized and reasonable values for the ligand field parameter, 10Dq, have been obtained. Crystal field bands could not be detected in the electronic spectra of these complexes, as they are obscured by the more intense charge transfer bands. Using the HMO approach for the interpretation of the electronic spectra in combination with the ligand field description of the charge transfer spectra we were able to calculate reasonable ligand field spectral parameters for all the complexes studied, as well as for the corresponding unsubstituted dithiobenzoate complexes. The calculated 10Dq values place the ligands under investigation at the upper end in the spectrochemical series of chelating dithio‐ligands, a fact which is consistent with the low‐spin type of these complexes.