Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

Abstract

Development of biomimetic catalytic systems that can imitate or even surpass natural enzymes remains an ongoing challenge 1–3. This is particularly true in the context of accessing non-natural reactions by bioinspired approaches, which offer intriguing possibilities for benign and affordable chemical synthesis 4. Exploiting the untapped potential of inorganic solids by translating complex knowledge in (bio)molecular-based systems may constitute a potentially useful strategy for such purpose 5, but efforts to capitalize on the minimum catalytic unit of a versatile solid matrix have been largely unsuccessful. Here, we show how an all-inorganic biomimetic system bearing robust nitrogen-neighboured 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 via the unprecedented aerobic oxidation of hydrosilane under ambient conditions is demonstrated. Moreover, this heterogeneous oxidase mimic also offers 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.