On-Water Surface Catalysis: From Hydrogen Bonding to Charge-Transfer Activation

Abstract

On-water catalysis accelerates reactions between poorly soluble organic substrates in aqueous suspensions, but its molecular origin remains debated. This Account argues that hydrogen bonding and proton transfer can both enhance charge-transfer stabilization between the organic reactants. Hydrogen bonds from surface water polarize the reacting complex, whereas protonation can perturb the same donor-acceptor interaction more strongly without requiring identical reaction pathways. We connect simulations of the water/vapor interface, finite-temperature cycloaddition studies, and energy decomposition analysis based on absolutely localized molecular orbitals. Dangling OH groups establish reactive contacts, but an increased transition-state hydrogen-bond count alone does not explain activation. Electronic analysis instead identified hydration-enhanced charge-transfer stabilization between organic partners by approximately 30%. Comparisons of related dienophiles, a protonated limiting model, and oxygen/sulfur substitution link substrate-dependent electronic response to hydration and bond formation. A hydration-induced charge-transfer response metric provides a testable molecular hypothesis, not a standalone measure of catalytic acceleration. Activation depends on differential stabilization of reactant and transition-state ensembles. Increasing the accessible reactive interface can amplify this local mechanism without requiring exceptionally strong additional electric fields, connecting conventional on-water chemistry with selected microdroplet reactions while distinguishing adsorption, concentration, and intrinsic molecular activation.