Paired Electrosynthesis at the Femtoliter Scale: Formation of 9,10-Anthracenedione from the Oxidation of Anthracene and Reduction of Dioxygen

A system is described in which the unique properties of a pair of microband electrodes are exploited both to initiate and to probe the products of a paired electrosynthesis using short-lived species. In particular, the oxidation of anthracene is coupled with the simultaneous reduction of dioxygen in acetonitrile to yield the anthracene radical cation and the superoxide anion. These latter react within a femtoliter scale volume to form initially 9,10-dihydro-9,10-epidioxyanthracene, which rearranges into 9,10-anthracenedione and, presumably, dihydrogen via an electron transfer catalyzed process.