SECTION OF CHEMICAL SCIENCES: SOLVOLYSIS OF ORGANOMERCURIALS*

The acid cleavage of triphenylvinylmercuric salts

“…Reaction of 1-HgOAc in MOAc in the presence of HC104 gave, Instead of the expected 1-OAc, a high yield of triphenylethylene (2). A similar reaction with 1-HgBr also gave 2.…”

“…Since such first-order dependence of the rate on HC104 concentrations of up to about it M has been utilized as a criterion on the nature of the ratedetermining step, some mechanistic significance for the presently observed second-order dependence on HC104 concentrations of up to about 3 M appears to be justified. If this is the case, the following is one possible n~echanism which would fit the observed result of d [2]…”

“…It is, therefore, of interest to generate a 'free' triphenylvinyl cation and to ascertain if 1,2-phenyl shifts would take place in such a species. In the solvolytic demercuration of alkylmercuric perchlorates, generally carried out by treating the alkylmercuric acetate in an appropriate solvent in the presence of HC104, free carbocations are believed to be senerated since the loss of HgO from RHg+ gives no co~~nterion for ionpair formation (2). In an attempt to senerate the triphenylvinyl cation, the possibility of solvolyzing triphenylvinylmercuric acetate (I-HgOAc) was studied.…”