水与超分子胶囊的相互作用对金的还原消除反应的催化作用
Interplay of Water and a Supramolecular Capsule for Catalysis of Reductive Elimination Reaction from Gold
摘要：
超分子组装体由于其明显的催化反应能力和天然酶的效率而获得了极大的关注。利用Born-Oppenheimer分子动力学和密度泛函理论，我们确定了超分子组装体Ga $_4$ L $_{612-}$对金配合物还原消除反应的催化能力的来源及其与酶的相似性。通过比较在明确的溶剂中的催化和未催化的反应，以确定反应物，过渡态，和产品的反应自由能，我们确定，催化部分-封装的水分子-产生电场，有助于显着降低活化自由能。虽然这与通过直接的主体-客体相互作用进行催化的仿生方案不同，但是纳米笼主体预先调节过渡态，以使其对投射到断裂碳键上的电场更敏感，从而以更高的催化效率完成还原消除反应。然而，它也表明，纳米笼组织不良的界面水，这反过来又产生电场，与衬底的断裂键错位，从而确定新的机会，在纳米笼组件的催化设计改进。
英文摘要：
Supramolecular assemblies have gained tremendous attention due to their apparent ability to catalyze reactions with the efficiencies of natural enzymes. Using Born-Oppenheimer molecular dynamics and density functional theory, we identify the origin of the catalytic power of the supramolecular assembly Ga$_4$L$_{612-}$ on the reductive elimination reaction from gold complexes and their similarity to enzymes. By comparing the catalyzed and uncatalyzed reaction in explicit solvent to identify the reaction free energies of the reactants, transition states, and products, we determine that a catalytic moiety -- an encapsulated water molecule -- generates electric fields that contribute significant reduction in the activation free energy. Although this is unlike the biomimetic scenario of catalysis through direct host-guest interactions, the nanocage host preconditions the transition state for greater sensitivity to electric field projections onto the breaking carbon bonds to complete the reductive elimination reaction with greater catalytic efficiency. However it is also shown that the nanocage poorly organizes the interfacial water, which in turn creates electric fields that misalign with the breaking bonds of the substrate, thus identifying new opportunities for catalytic design improvements in nanocage assemblies.
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