Bridged Mercurinium Ion

A bridged mercurinium ion is a three-membered, cyclic organomercury intermediate formed when a mercury electrophile adds across a carbon–carbon double bond. In oxymercuration, the alkene attacks Hg(OAc)⁺, creating bonds between mercury and both alkene carbons while the positive charge is shared within the bridge; nucleophilic water then attacks the more substituted carbon, typically from the opposite face. Subsequent deprotonation and reductive demercuration convert the intermediate into an alcohol, usually with Markovnikov regioselectivity and without carbocation rearrangement. This mechanism helps explain the synthetic value of oxymercuration–demercuration for preparing alcohols from alkenes under mild conditions.

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