X-ray photoelectron spectra of tetraaza macrocyclic complexes of cobalt with molecular oxygen

X-ray photoelectron spectroscopy has been used to determine the electronic state of the cobalt-molecular-oxygen fragment, the type of coordination, and, in some cases, the nature of the bond between the central ion and the axial ligand in the complexes Co^II(htd)(NCS))C10₄, -O₂{Co(htd((X)}₂](ClO₄)₂ (X=NCS^–, N₃ ^–, NCO^–, OH^–), and O₂{Co(htd)(Im)}₂](ClO₄)₄. It has been established that the NCO^– and NCS^– ligands are coordinated as electron donors in an axial position by means of their nitrogen atoms. A conclusion regarding the electronic structure of the Co^III-O₂ ^2–-Co^III fragment has been drawn on the basis of an analysis of the binding energy (E_b) of the Co 2p_3/2 electrons in the oxygenated complexes and in the corresponding low-spin cobalt(II) compounds and cobalt(III) compounds.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 4, pp. 437–442, July–August, 1990.