Interfacial Water Mediates Oligomerization Pathways of Monoterpene Carbocations

The air-water interface plays central roles in "on-droplet" synthesis, living systems, and the atmosphere; however, what makes reactions at the interface specific is largely unknown. Here, we examined carbocationic reactions of monoterpene (C₁₀H₁₆ isomer) on an acidic water microjet by using spray ionization mass spectrometry. Gaseous monoterpenes are trapped in the uppermost layers of a water surface via proton transfer and then undergo a chain-propagation reaction. The oligomerization pathway of β-pinene (β-P), which showed prompt chain-propagation, is examined by simultaneous exposure to camphene (CMP). (CMP)H⁺ is the most stable isomer formed via rearrangement of (β-P)H⁺ in the gas phase; however, no co-oligomerization was observed. This indicates that the oligomerization of (β-P)H⁺ proceeded via ring-opening isomerization. Quantum chemical calculations for [carbocation-(H₂O)] complexes revealed that the ring-opened isomer is stabilized by hydrogen-π bonds. We propose that partial hydration is a key factor that makes the interfacial reaction unique.