Bifunctional Carbenium Dications as Metal-Free Catalysts for the Reduction of Oxygen

The development of catalysts for the oxygen reduction reaction is a coveted objective of relevance to energy research. This study describes a metal-free approach to catalyzing the reduction of O-2 into H2O2, based on the use of redox-active carbenium species. The most active catalysts uncovered by these studies are the bifunctional dications 1,8-bis(xanthylium)-biphenylene ([3](2+)) and 4,5-bis(xanthylium)-9,9-dimethylxanthene ([4](2+)) which promote the reaction when in the presence of decamethylferrocene and methanesulfonic acid. Electrochemical studies carried out with [4](2+) suggest the intermediacy of an organic peroxide that, upon protonation, converts back into the starting dication while also releasing H2O2. Kinetic studies point to the second protonation event as being rate-determining.