Probing the Transition State-to-Intermediate Continuum: Mechanistic Distinction between a Dry versus Wet Perepoxide in the Singlet Oxygen "Ene" Reaction at the Air-Water Interface

A mechanistic study is reported for the reactions of singlet oxygen (O-1(2)) with alkene surfactants of tunable properties. Singlet oxygen was generated either top-down (photochemically) by delivery as a gas to an air-water interface or bottom-up (chemically) by transport to the air-water interface as a solvated species. In both cases, reactions were carried out in the presence of 7-carbon (7C), 9-carbon (9C), or 11-carbon (11C) prenylsurfactants [(CH3)(2)C=CH(CH2)(n)SO3- Na+ (n = 4, 6, 8)]. Higher "ene" hydroperoxide regioselectivities (secondary ROOH 2 to tertiary ROOH 3) were reached in delivering O-1(2) top down through air as compared to bottom-up via aqueous solution. In the photochemical reaction, ratios of 2:3 increased from 2.5:1 for 7C, to 2.8:1 for 9C, and to 3.2:1 for 11C. In contrast, in the bubbling system that generated O-1(2) chemically, the selectivity was all but lost, ranging only from 1.3:1 to 1:1. The phase-dependent regioselectivities appear to be correlated with the "ene" reaction with photochemically generated, drier O-1(2) at the air-water interface vs those with wetter O-1(2) from the bubbling reactor. Density functional theory-calculated reaction potential energy surfaces (PESs) were used to help rationalize the reaction phase dependence. The reactions in the gas phase are mediated by perepoxide transition states with 32-41 kJ/mol binding energy for C=C(pi)center dot center dot center dot O-1(2). The perepoxide species, however, evolve to well-defined stationary structures in the aqueous phase, with covalent C-O bonds and 85-88 kJ/mol binding energy. The combined experimental and computational evidence points to a unique mechanism for O-1(2) "ene" tunability in a perepoxide continuum from a transition state to an intermediate.