Single-electron transfer upon formation of 2,2,3,3-tetracyano-1-phenyl-7,8-dithiabicyclo[3.2.1]octane from allyl dithiobenzoate and tetracyanoethylene. Electrochemical investigations

Studies by the method of cyclic potential scanning from 0.2 to 1.9 V provid ed electroanalytical evidence that the reaction of allyl dithiobenzoate wit h tetracyanoethylene (TCNE) in MeCN proceeds as the reaction of the TCNE.- radical anion with the PhSSAl1(.+) radical cation to form phenyl-substitute d 2,2,3,3-tetracyano-7,8-dithiabicydo[3.2.1]octane. When current is not app lied, the reaction does not proceed at 20 degrees C for 3 days. However, th is reaction in boiling MeCN occurs without electrochemical activation and, apparently, involves intermediate formation of the above radical ions. It w as established by semiempirical PM3 calculations that allyl dithiobenzoate and TCNE form a stable charge-transfer complex that precedes chemical elect ron transfer.