Paramagnetic Cobalt(III) Complexes with Organic Ligands. VI. An X-Ray Photoelectron Spectroscopic Study

Abstract

Abstract Paramagnetic tetraammine-5-nitrosalicylato cobalt complex, paramagnetic μ-hyperoxo-dicobalt complexes and related diamagnetic compounds have been studied by X-ray photoelectron spectroscopy. In all these compounds, the binding energies of Co 2p electrons and their spin-orbit separation were those of usual Co(III) complexes. In the spectrum of paramagnetic tetraammine-5-nitrosalicylatocobalt salt, satellites appeared near the Co 2p peaks showing certain spin density at the cobalt atoms. At the same time, the C ls spectrum showed that considerable portion of carbon atoms has high binding energy suggesting delocalization of electron hole over the organic ligand. The O ls peaks in μ-hyperoxo complexes were ca. 0.6 eV higher than those in μ-peroxo complexes. Deconvolution of the O ls peak in the μ-OOH complex gave OH, =O–, and H2O peaks at the 1:1:1 ratio, supporting the μ-OOH formulation.