Nitrogen-Neighbored Single-Cobalt Sites Enable Heterogeneous Oxidase-Type Catalysis

The development of biomimetic catalytic systems that can imitate or even surpass natural enzymes remains an ongoing challenge, especially for bioinspired syntheses that can access non-natural reactions. Here, we show how an all-inorganic biomimetic system bearing robust nitrogen-neighbored single-cobalt site/pyridinic-N site (Co-N4/Py-N) pairs can act cooperatively as an oxidase mimic, which renders an engaged coupling of oxygen (O2) reduction with synthetically beneficial chemical transformations. By developing this broadly applicable platform, the scalable synthesis of greater than 100 industrially and pharmaceutically appealing O-silylated compounds including silanols, borasiloxanes, and silyl ethers via the unprecedented aerobic oxidation of hydrosilane under ambient conditions is demonstrated. Moreover, this heterogeneous oxidase mimic also offers the potential for expanding the catalytic scope of enzymatic synthesis. We anticipate that the strategy demonstrated here will pave a new avenue for understanding the underlying nature of redox enzymes and open up a new class of material systems for artificial biomimetics.

Automated summary

The study presents a biomimetic system that can imitate or surpass natural enzymes for bioinspired syntheses of non-natural reactions. Through the development of this widely applicable platform, the scalable synthesis of over 100 industrially and pharmaceutically appealing O-silylated compounds is demonstrated. This heterogeneous oxidase mimic also has potential for expanding the catalytic scope of enzymatic synthesis.