Mechanistic Studies on TiO 2 Photoelectrochemical Radical Cation [2 + 2] Cycloadditions

Abstract

In addition to electrochemical and photochemical approaches, the photoelectrochemical method using semiconductors as photoelectrodes is a third type of approach in the field of synthetic organic chemistry that enables precise control of single electron transfer (SET) reactions. Herein, we report mechanistic studies on TiO 2 photoelectrochemical redox neutral reactions, where both reductive and oxidative SET are involved, using radical cation [2 + 2] cycloadditions as models. In the presence of platinum nanoparticles or molecular oxygen as electron sink or electron acceptor, respectively, the mechanistic details for the photoelectrochemical reactions can be investigated because the excited electron at the conduction band of TiO 2 is removed.