Secondary Hydrogen Isotope Effects on Deoxymercuration1

Abstract

Secondary isotope effects on the rate of acid-induced deoxymercuration of 2-phenyl-2-methoxyethylmercuric iodide were studied. Deuterium substitution at the 2carbon gives k/sub H//k/sub D/, 1.12. Deuterium substitution at the 1- carbon gives k/sub H//k/sub D/, 0.91. The latter is one of a small number of inverse isotope effects that were observed. From these and results previously presented it was concluded that the deoxymercuration transition state has a partial positive charge on the carbon from which oxygen is leaving and also has some olefin-mercuric iodide complex character. (auth)