The redox behavior of gem-dihalo compounds: 9,9-dibromofluorene, 9,9-dichlorofluorene and dichlorodiphenylmethane

The redox behavior of several gem-dihalo compounds has been examined at platinum and vitreous carbon electrodes in dimethylformamide. The reduction of 9,9-dichlorofluorene is initially an overall two-electron process which involves cleavage of chloride ion and the formation of 9-chlorofluorenyl anion. The final products and their distribution are then dependent upon the relative rates of reduction of the parent compound, nucleophilic attack of 9-chlorofluorenyl anion on the parent compound, and proton availability. If reaction by substitution is permitted to predominate, 9,9′-dichlorobifluorenyl results. This species is electroactive at the applied potential and undergoes reductive dechlorination to give bifluorenylidene. In contrast, if either the rate of reduction of 9,9-dichlorofluorene of the rate of protonation of 9-chlorofluorenyl anion exceeds the rate of substitution, the predominant product becomes 9-chlorofluorene. Reduction of this species then gives a mixture of fluorene and bifluorenyl when electrolysis is effected in an aprotic medium and fluorene when electrolysis is performed in the presence of diethyl malonate, a weak proton donor. Dichlorodiphenylmethane and 9,9-dibromofluorene also undergo reductive dehalogenation to give monomeric and dimeric products by pathways analogous to those observed for dichlorofluorene. In the case of dibromofluorene, however, the product distribution is also potential dependent since the intermediate 9-bromofluorenyl radical may not be reduced at the applied potential. No evidence was obtained in these studies to support previous claims of carbenes and/or carbene radical anions in these reductions.