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Supramolecular assemblies have gained tremendous attention due to theirapparent ability to catalyze reactions with the efficiencies of naturalenzymes. Using Born-Oppenheimer molecular dynamics and density functionaltheory, we identify the origin of the catalytic power of the supramolecularassembly Ga$_4$L$_{612-}$ on the reductive elimination reaction from goldcomplexes and their similarity to enzymes. By comparing the catalyzed anduncatalyzed reaction in explicit solvent to identify the reaction free energiesof the reactants, transition states, and products, we determine that acatalytic moiety -- an encapsulated water molecule -- generates electric fieldsthat contribute significant reduction in the activation free energy. Althoughthis is unlike the biomimetic scenario of catalysis through direct host-guestinteractions, the nanocage host preconditions the transition state for greatersensitivity to electric field projections onto the breaking carbon bonds tocomplete the reductive elimination reaction with greater catalytic efficiency.However it is also shown that the nanocage poorly organizes the interfacialwater, which in turn creates electric fields that misalign with the breakingbonds of the substrate, thus identifying new opportunities for catalytic designimprovements in nanocage assemblies.

Interplay of Water and a Supramolecular Capsule for Catalysis of Reductive Elimination Reaction from Gold