The significance of the "mercurinium ion" in oxymercuration.

Abstract

The complex formed by mercuric nitrate with cyclohexene seems not to resemble similar argentous, cuprous, and platinous salt complexes, since it is stabilized by nitric acid while they are decomposed by acidic media. Furthermore, the cyclohexene – mercuric nitrate – nitric acid system is not stable as are the others in absence of air but decomposes to yield two equivalents of mercurous salt and one equivalent of formylcyclopentane. One or both of these products are presumed to be the material which earlier workers by implication defined as 1-hydroxy-2-nitratomercuricylohexane. It has now been found that this product could not have been formed under the reaction conditions used by these earlier workers. Finally the solubilization of cyclohexene in aqueous mercuric nitrate, on which the earlier workers based their concept of an alkene-mercurinium ion, does not have its counterpart in the solubilization of cyclohexene in aqueous mercuric acetate, since the rate of solution in the latter case is not faster than the rate of hydroxymercuration. In consequence there is no present evidence that such an ion is involved in oxymercuration of alkenes.