化学
反应性(心理学)
位阻效应
氢化物
配体(生物化学)
星团(航天器)
卡宾
结晶学
计算化学
催化作用
立体化学
金属
有机化学
医学
生物化学
替代医学
受体
病理
计算机科学
程序设计语言
作者
Andrew W. Beamer,Joshua A. Buss
摘要
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 Cu3Hx 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.
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