CYCLOHEPTATRIENE RADICAL-ANION

The reduction of cycloheptatriene (1) and some related trienes in aprotic solvents at a platinum electrode was studied by cyclic voltammetry and controlled-potential coulometry. A reversible wave at -2.5 eV for the production of the radical anion of 1 was observed in ammonia containing 0.1 KI. Quasi-reversible or irreversible reduction was observed in acetonitrile and N,N-dimethylformamide. The radical anion was stable in ammonia on the voltammetric time scale but decayed slowly by disproportionation and coupling reaction pathways to giw respectively 1,3- and 1,4-cycloheptadienes and C14H18 isomers which incorporate bitropyl carbon skeleta. The chemical fate of 1 radical anion is discussed, as is the difference in reaction course for electrochemical and dissolving-metal reductions in ammonia. © 1979, American Chemical Society. All rights reserved.