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Published on: August 18, 2012
Oxidizable Ketones: Persistent Radical Cations from the Single-Electron Oxidation of 2,3-Diaminocyclopropenones
Zack M Strater1, Michael Rauch1, Steffen Jockusch1
1Department of Chemistry, Columbia University, New York, NY, 10027, USA.
Abstract:
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.
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