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This article presents a retrospective account of our group’s heterobinuclear (NHC)Cu-[MCO] catalyst design concept (NHC = N-heterocyclic carbene, [MCO] = metal carbonyl anion), the discovery of its application towards UV-light-induced dehydrogenative borylation of unactivated arenes, and the subsequent pursuit of thermal reaction conditions through structural modifications of the catalysts. The account highlights advantages of using a hypothesis-driven catalyst design approach that, while often fruitless with regard to the target transformation in this case, nonetheless vastly expanded the set of heterobinuclear catalysts available for other applications. In other words, curiosity-driven research conducted in a rational manner often provides valuable products with unanticipated applications, even if the primary objective is viewed to have failed. 1 Introduction to Heterobinuclear Catalysts for C–H Borylation 2 Pursuit of Thermal Borylation Conditions 3 Catalysts beyond Copper Carbenes 4 Conclusions 

A review of metal-catalysed carbonylation reactions involving single-electron transfer mechanisms and organic radical intermediates is presented, emphasizing new avenues to carbonyl compounds that are enabled by this approach. Catalyst-induced, oxidant-induced, and photo-induced radical carbonylations are discussed, as are atom-transfer carbonylation chain processes. Collectively, this body of carbonylative coupling chemistry complements more traditional precious metal-based catalytic systems that engage in substrate carbonylation by two-electron pathways.