Comparing the peroxo/superoxo nature of the interaction between molecular O2 and β-diketiminato-copper and nickel complexes

Abstract

Adducts resulting from the interaction between molecular oxygen and β-diketiminato-copper and nickel complexes have been recently described in the literature as peroxo and superoxo complexes, respectively. The nature of the interaction is analyzed by means of DDCI calculations and an orthogonal valence bond reading of the ground state wavefunction for each system. Our results reveal that there is not any substantial difference between these systems, both presenting a marked leading superoxo nature, which is in line with the fact that LCu-O(2) and LNi-O(2) adducts present similar O-O distances and quite close O-O stretching vibration modes.