Tuning the 1O2 Oxidation of a Phenol at the Air/Solid Interface of a Nanoparticle: Hydrophobic Surface Increases Oxophilicity

Abstract

Although silica surfaces have been used in organic oxidations for the production of peroxides, studies of airborne singlet oxygen at interfaces are limited and have not found widespread advantages. Here, with prenyl phenol-coated silica and delivery of singlet oxygen (¹O₂) through the gas phase, we uncover significant selectivity for dihydrofuran formation over allylic hydroperoxide formation. The hydrophobic particle causes prenyl phenol to produce an iso-hydroperoxide intermediate with an internally protonated oxygen atom, which leads to dihydrofuran formation as well as O atom transfer. In contrast, hydrophilic particles cause prenyl phenol to produce allylic hydroperoxide, due to phenol OH hydrogen bonding with SiOH surface groups. Mechanistic insight is provided by air/nanoparticle interfaces coated with the prenyl phenol, in which product yield was 6-fold greater on the hydrophobic nanoparticles compared to the hydrophilic nanoparticles and total rate constants (ASI-k_T) of ¹O₂ were 13-fold greater on the hydrophobic vs hydrophilic nanoparticles. A slope intersection method was also developed that uses the airborne ¹O₂ lifetime (τ_airborne) and surface-associated ¹O₂ lifetime (τ_surf) to quantitate ¹O₂ transitioning from volatile to non-volatile and surface boundary (surface···¹O₂). Further mechanistic insights on the selectivity of the reaction of prenyl phenol with ¹O₂ was provided by density functional theory calculations.