Synthesis, Structural Characterization, and CO2Reactivity of a Constitutionally Analogous Series of Tricopper Mono-, Di-, and Trihydrides

The formation of hydrides at heterogeneous copper surfaces results in dramatic structural and reactivity changes, yet the morphologies of these materials and their respective roles in catalysis are not well understood. Of particular interest is the reactivity of heterogeneous copper hydrides with carbon dioxide (CO₂), an early mechanistic branching point in the CO₂ reduction reaction. Herein, we report the synthesis, characterization, and reactivity of tricopper compounds supported by a facially biased, chelating tris(carbene) ligand scaffold. This sterically bulky environment affords access to an isolable series of tricopper hydrides: [LCu₃H]²⁺ (4), [LCu₃H₂]⁺ (3), and LCu₃H₃ (6). Single-crystal X-ray diffraction and solution NMR spectroscopy studies reveal both geometric flexibility within the Cu₃ core and fluxionality of hydride ligands across the Cu₃ cluster, providing both atomically precise experimental analogues of static surface species and emulating dynamic ligand behavior proposed for surfaces. Electronic structure calculations serve as a predictor of hydricity, which was likewise benchmarked experimentally via both protonolysis and hydride abstraction reactions. Increased hydride number (and commensurately lower cluster charge) results in more hydridic complexes, with a thermodynamic hydricity range spanning >30 kcal/mol. These thermochemical studies serve as an accurate predictor of CO₂ reactivity. Together, this Cu₃H_x series exhibits the structure/reactivity relationships proposed for catalytically active copper surfaces, validating the application of carefully designed molecular clusters toward elucidating mechanisms in surface science.