Our study investigated Co-catalyzed C─H borylation of arenes using a terpyridine ligand from a theoretical standpoint. Through computation, we elucidated the overall mechanism including C─H activation, C─B formation, and catalyst regeneration. In addition, we addressed issues of catalyst stability, and conducted comparative analyses with related Ir-catalyzed systems.

Abstract

Co-catalyzed C─H borylation of arenes has drawn great attention in organic chemistry, in which the system using terpyridine (tpy) ligands stands out due to its bench stability and synthetic accessibility. However, despite its experimental breakthrough, it remained largely unexplored from a theoretical standpoint. In this work, we present a comprehensive theoretical investigation into the cobalt-catalyzed C─H borylation of arenes using terpyridine as ligand. Our computational analysis reveals the overall mechanism involving stages as C─H activation, C─B formation, and catalyst regeneration, with C─H activation identified as the rate-determining step. Furthermore, we attempt to address the reactivity issue, the key challenges faced by this system, including potential catalyst deactivation mechanisms and comparative analysis with other related catalytic systems.