Theoretical study of the formation of metal–oxo species of the first transition series with the ligand 14-TMC: driving factors of the “Oxo Wall”

O⋯O bond cleavage. DFT calculations reveal that the barrier for O⋯O bond cleavage is higher with the late transition metals (Co, Ni, and Cu) than the early transition metals (Cr, Mn, and Fe), and the formed late metal-oxo species are also thermodynamically less stable. The higher barrier may be due to electronic repulsion because of the pairing of d electrons. In the late transition metal series, the electron goes into an antibonding orbital, which decreases the bond order and hence decreases the possibility of metal-oxo formation. Computed structural parameters and spin densities suggest that valence tautomerism occurs in the late transition metal-oxo species which remain as a metal-oxyl. Our findings support the concept of the "Oxo Wall".