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Oxidizable Ketones: Persistent Radical Cations from the Single‐Electron Oxidation of 2,3‐Diaminocyclopropenones.
Author(s) -
Strater Zack M.,
Rauch Michael,
Jockusch Steffen,
Lambert Tristan H.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201902265
Subject(s) - electron paramagnetic resonance , heteroatom , chemistry , radical ion , cyclic voltammetry , ion , metal , photochemistry , ligand (biochemistry) , electron , oxygen , electrochemistry , crystallography , medicinal chemistry , inorganic chemistry , ring (chemistry) , organic chemistry , electrode , nuclear magnetic resonance , biochemistry , physics , receptor , quantum mechanics
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.