Oxidizable Ketones: Persistent Radical Cations from the Single-Electron Oxidation of 2,3-Diaminocyclopropenones.

Single electron oxidation of 2,3-diaminocyclopropenones is shown to give rise to stable diaminocyclopropenium oxyl (DACO) radical cations. Cyclic voltammetry reveals reversible oxidations in the range of +0.70-1.10 V (vs. SCE). Computational, EPR, and X-ray analysis support the view that the oxidized species is best described as a cyclopropenium ion with spin density located on the heteroatom substituents, including 23.5 % on oxygen. The metal-ligand behavior of the DACO radical is also described.