Synthesis, Structural, and Spectroscopic Characterization and Reactivities of Mononuclear Cobalt(III)−Peroxo Complexes

Metal−dioxygen adducts are key intermediates detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. In this study, mononuclear cobalt(III)−peroxo complexes bearing tetraazamacrocyclic ligands, [Co(12-TMC)(O2)]+ and [Co(13-TMC)(O2)]+, were synthesized by reacting [Co(12-TMC)(CH3CN)]2+ and [Co(13-TMC)(CH3CN)]2+, respectively, with H2O2 in the presence of triethylamine. The mononuclear cobalt(III)−peroxo intermediates were isolated and characterized by various spectroscopic techniques and X-ray crystallography, and the structural and spectroscopic characterization demonstrated unambiguously that the peroxo ligand is bound in a side-on η2 fashion. The O−O bond stretching frequency of [Co(12-TMC)(O2)]+ and [Co(13-TMC)(O2)]+ was determined to be 902 cm−1 by resonance Raman spectroscopy. The structural properties of the CoO2 core in both complexes are nearly identical; the O−O bond distances of [Co(12-TMC)(O2)]+ and [Co(13-TMC)(O2)]+ were 1.4389(17) Å and 1.438(6) Å, respectively. The cobalt(III)−peroxo complexes showed reactivities in the oxidation of aldehydes and O2-transfer reactions. In the aldehyde oxidation reactions, the nucleophilic reactivity of the cobalt−peroxo complexes was significantly dependent on the ring size of the macrocyclic ligands, with the reactivity of [Co(13-TMC)(O2)]+ > [Co(12-TMC)(O2)]+. In the O2-transfer reactions, the cobalt(III)−peroxo complexes transferred the bound peroxo group to a manganese(II) complex, affording the corresponding cobalt(II) and manganese(III)−peroxo complexes. The reactivity of the cobalt−peroxo complexes in O2-transfer was also significantly dependent on the ring size of tetraazamacrocycles, and the reactivity order in the O2-transfer reactions was the same as that observed in the aldehyde oxidation reactions.