Abstract
The reaction of hydroxymercurated propene with sodium nitrite in aqueous solution [CH 3CH(OH)CH 2HgCl0 2 + NaNO 2 → CH 3CH(NO 2)CH 2HgClO 4 + NaOH] has been investigated by following the reaction in situ by PMR. The amount of the mercurial coordinated by the nitrite ions was evaluated by analyzing the geminal 199Hg 1H spin-coupling constant, and thereby rate equations were determined for both aquo- and nitrito-mercurials. The observed values of secondary deuterium isotope effects are explained in conformity with the mercurinium ion mechanism suggested previously. Activation parameters for aquo- and nitrito-mercurials are discussed in terms of ligand properties.
Published Version
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