Abstract
It is shown that there are four possible electronic configurations for the ground-state of the dioxygen complex of Co(acacen)L (with the fifth ligand L = none, H2 O, Imidazole, CN− and CO). Fromab-initio calculations with a minimal basis set, close energy values are indeed computed for these four configurations with the lowest one (ground state configuration) corresponding to a charge-transfer configuration Co(III)-O −2 2, in agreement with the results of ESR spectroscopy from the literature. The enthalpy of oxygenation is related to the σ-donor ability of the fifth ligand and to the ease of oxydation of Co(II) to Co(III).
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Dedieu, A., Veillard, A. Electronic aspects of dioxygen binding to cobalt-schiff-base-complexes: Anab initio calculation. Theoret. Chim. Acta 36, 231–235 (1975). https://doi.org/10.1007/BF00572564
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DOI: https://doi.org/10.1007/BF00572564