Catalytic dioxygen reduction mediated by a tetranuclear cobalt complex supported on a stannoxane core

The synthesis, spectroscopic characterization (infrared, electron paramagnetic resonance and X-ray absorption spectroscopies) and density functional theoretical calculations of a tetranuclear cobalt complex Co₄L1 involving a nonheme ligand system, L1, supported on a stannoxane core are reported. Co₄L1, similar to the previously reported hexanuclear cobalt complex Co₆L2, shows a unique ability to catalyze dioxygen (O₂) reduction, where product selectivity can be changed from a preferential 4e^-/4H⁺ dioxygen-reduction (to water) to a 2e^-/2H⁺ process (to hydrogen peroxide) only by increasing the temperature from -50 to 30 °C. Detailed mechanistic insights were obtained on the basis of kinetic studies on the overall catalytic reaction as well as by low-temperature spectroscopic (UV-Vis, resonance Raman and X-ray absorption spectroscopies) trapping of the end-on μ-1,2-peroxodicobalt(iii) intermediate 1. The Co₄L1- and Co₆L2-mediated O₂-reduction reactions exhibit different reaction kinetics, and yield different ratios of the 2e^-/2H⁺ and 4e^-/4H⁺ products at -50 °C, which can be attributed to the different stabilities of the μ-1,2-peroxodicobalt(iii) intermediates formed upon dioxygen activation in the two cases. The deep mechanistic insights into the transition-metal mediated dioxygen reduction process that are obtained from the present study should serve as useful and broadly applicable principles for future design of more efficient catalysts in fuel cells.