Optimization of Metal-Support Cooperation for Boosting the Performance of Supported Gold Catalysts for the Borylation of C-O and C-N Bonds.

The cooperation of multiple catalytic components is a powerful tool for intermolecular bond formation, specifically, cross-coupling reactions. Supported metal catalysts have interfacial sites between metal nanoparticles and their supports where multiple catalytic elements can work in cooperation to efficiently promote intermolecular reactions. Hence, the establishment of novel guidelines for designing active interfacial sites of supported metal catalysts is indispensable for heterogeneous catalysts which enable efficient cross-coupling reactions. In this article, we performed kinetic and theoretical studies to elucidate the effect of metal-support cooperation for the borylation of C-O bonds by supported gold catalysts and revealed that the Lewis acid density of the supports determined the number of active sites at which metal nanoparticles (NPs) and Lewis acid at the surface of the supports work in cooperation. Furthermore, DFT calculations revealed that strong adsorption of diborons at the interface between Au NPs and supports and a decrease in the LUMO level of adsorbed diboron were responsible for efficient C-O bond borylation. Supported Au catalysts with the optimized metal-metal oxide cooperation sites, namely, Au/α-Fe 2 O 3 catalyst, showed excellent activity for C-O bond borylation, and also enabled the synthesis of organoboron compounds by using continuous-flow reactions. Furthermore, Au/α-Fe 2 O 3 showed high activity for direct C-N bond borylation without the transformation of amino groups to ammonium cations. The results described herein suggest that the optimization of metal-metal oxide cooperation is beneficial for taking full advantage of the potential performance of supported metal catalysts for intermolecular reactions.