Molecular orbital study of coordinated dioxygen VII. Dioxygen activation on cyanate complexes of Mn, Fe, Co, Ni and Cu

Abstract

Dioxygen complexes of the type κ[M(CN) 5(O 2)] q were investigated by the CNDO/3-UHF method of MO/3-LCAO/3-SCF calculations. Five central atoms M, three oxidation states q, and two spin states κ, yield 30 combinations under study. The dioxygen activation is described in terms of the local electron configuration of the dioxygen π antibonding orbitals. The Wiberg indices, charge distributions and energy partitioning complete this description. The complexes studied were classified into three groups depending on the degree of dioxygen activation. A limited geometry variation for the 2[Co(CN) 5(O 2)] 3− complex was also performed.