Oxymercuration of alkenes follows Markovnikov's rule, but why? (I got some answers like the resonance structures of mercurinium ion are sometimes likely to have positive charge on more substituted carbon. But I don't know what those structures be like and how this whole phenomenon is happening.)


1 Answer 1


You should read mechanism section of oxymercuration of alkenes on Wikipedia. For your convenience, see the 3-step mechanism given in there:


Now, if you ask yourself a question, "why $\ce{H2O}$ is attacking more substituted carbon center in second step?" You'd get the answer to your own question.

See step-wise mechanism, which shows why more substituted carbon has positive charge.

step-wise mechanism

  • $\begingroup$ the mechanism posted in the last segment does not seem to have applied the concept of formation of mercurinium complex (an intermediate complex formed in the due course of oxymercuration-demercuration process), does it hold authenticity? $\endgroup$ Apr 23, 2018 at 15:30
  • $\begingroup$ +1 for what OP said: the stepwise mechanism does not proceed through the mercurinium ion intermediate. $\endgroup$ Nov 27, 2020 at 14:41
  • $\begingroup$ No body claims these step-wise mechanisms are existed during chemical reactions. They were presented to explain the results. Sometimes, intermediates were isolated to confirm the mechanism. $\endgroup$ Nov 27, 2020 at 15:39

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