MECHANISM OF CONVERSION OF 1-1 ANION-RADICAL SALTS OF TETRACYANO-PARA-QUINODIMETHANE TO THEIR 1-2 ANALOGS

Some anion-radical salts of TCNQ with composition D+TCNQ-. can be converted to their complex analogues, D+TCNQ-TCNQ0, by simple recrystallization from pure acetonitrile. This conversion proceeds through dispro-portionation of TCNQ-, which produces TCNQ0and TCNQ2-. TCNQ0is incorporated into D+TCNQ-forming the 1:2 salt. TCNQ2-is irreversibly oxidized to α,α-dicyano-p-toluoyl ion, DCTC-, a process which comprises the driving force for the overall conversion mechanism. In cases where some formation of a 1:2 analogue occurs in the attempted synthesis of a 1:1 salt, rigorous exclusion of Oo from the preparation causes exclusive production of the simple analogue. Copyright © 1979, American Chemical Society. All rights reserved.