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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 [ABSTRACT FROM AUTHOR]

Bimetallic effects on stoichiometric β-hydride elimination and migratory insertion reactions were examined. Bimetallic reaction conditions drove β-hydride elimination at Cu, while bimetallic C–B elimination occurred in the absence of β-hydrogens. The inherent migratory insertion chemistry of alkynes at Ni was diverted under bimetallic reaction conditions to favor C–H deprotonation. [ABSTRACT FROM AUTHOR]

The Ca 2+ solvation structure at the electrolyte/electrode interface is of central importance to understand electroreduction stability and solid-electrolyte interphase (SEI) formation for the novel multivalent Ca battery systems. Using an exemplar electrolyte, the concentration-dependent solvation structure of Ca(BH 4 ) 2 -tetrahydrofuran on a gold model electrode has been investigated with various electrolyte concentrations via electrochemical quartz crystal microbalance with dissipation (EQCM-D) and X-ray photoelectron spectroscopy (XPS). For the first time, in situ EQCM-D results prove that the prevalent species adsorbed at the interface is CaBH 4 + across all concentrations. As the salt concentration increases, the number of BH 4 - anions associated with Ca 2+ increases, and much larger solvated complexes such as CaBH 4 + ·4THF or Ca(BH 4 ) 3 - ·4THF form at the interface at high concentrations prior to Ca plating. Different interfacial chemistries lead to the formation of SEIs with different components demonstrated by XPS. High electrolyte concentrations reduce the solvent decomposition and promote the formation of thick, uniform, and inorganic-rich (i.e., CaO) SEI layers, which contribute to improved Ca plating efficiency and current density in electrochemical measurements.