2022 Volume 65 Issue 4 Pages 134-139
Coordination chemistry has established the principle of “organometallic smart design: metal × ligand” for metal complexes with specific properties and functions based on empirical rules and quantum chemistry considerations. Numerous metal complexes have subsequently been synthesized to catalyze required chemical reactions. This review describes several representative studies, especially concerning the reactions of designed metal complexes with dioxygen, dihydrogen, and methane gases. Copper-mediated dioxygen activation and nickel–iron-mediated dihydrogen activation were inspired by the enzymatic activities of tyrosinase and nickel–iron hydrogenase. Hydroxylation of arene ring, epoxidation of styrene, and oxidation of carbon–hydrogen bonds of hydrocarbons have been achieved using a dinuclear copper peroxide complex derived from dioxygen modelled on tyrosinase. Biomimetic dihydrogen oxidation and dioxygen reduction have been promoted by nickel–iron and nickel–ruthenium complexes in organic solvent and water, based on the oxygen-tolerant nickel–iron hydrogenase. The transformation of methane to methanol and formaldehyde using dioxygen as an oxidant has been achieved by input of light energy into a designed diruthenium dioxide complex.
