Carbocations

Vinyl cation

The vinyl cation is a carbocation with the positive charge on an alkene carbon. Its empirical formula is C2H+3. More generally, a vinylic cation is any disubstituted, trivalent carbon, where the carbon bearing the positive charge is part of a double bond and is sp hybridized. In the chemical literature, substituted vinylic cations are often referred to as vinyl cations, and understood to refer to the broad class rather than the C2H+3 variant alone. The vinyl cation is one of the main types of reactive intermediates involving a non-tetrahedrally coordinated carbon atom, and is necessary to explain a wide variety of observed reactivity trends. Vinyl cations are observed as reactive intermediates in solvolysis reactions, as well during electrophilic addition to alkynes, for example, through protonation of an alkyne by a strong acid. As expected from its sp hybridization, the vinyl cation prefers a linear geometry. Compounds related to the vinyl cation include allylic carbocations and benzylic carbocations, as well as aryl carbocations. Compared to other reactive intermediates such as radicals and carbanions, the vinyl cation long remained poorly-understood and were initially thought to be too high energy to form as reactive intermediates. Vinyl cations were first proposed in 1944 as a reactive intermediate for the acid-catalyzed hydrolysis of alkoxyacetylenes to give alkyl acetate. In the first step of their facile hydration reaction, which was the rate limiting step, a vinyl cation reactive intermediate was proposed; the positive charge was believed to formally lie on a dicoordinate carbon. This is the first time such a transition state can be found in the literature. (Wikipedia).

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Related pages

Carbocation | Orbital hybridisation | Carbanion | Nonaflate