Instability of vinylic and arylic carbocations

I have checked the net a lot and read quite a few books, but I still am not able to
understand why vinylic and arylic carbocations are so unstable. Can someone
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For arylic carbocation, the carbon bearing postive charge cannot participate in
3
resonance with adjacent carbons because it's p orbital is perpendicular to the other
orbitals. I didn't really understand this. This is what I found while surfing the net

Background

S-orbitals are lower in energy than p-orbitals, therefore the more s-character in an orbital, the
lower its energy and the more stable any electrons occupying the orbital. In other words,
electrons will be more stable (lower in energy) in an sp orbital than an sp2 orbital, and electrons
in an sp2 orbital will be lower in energy than those in an sp3

orbital.

This is the basis of the inductive effect. For example, it explains why the electrons in an sp3

methyl group will be drawn towards a connected sp2 carbon in an aromatic ring - the methyl
group is inductively electron donating to the aromatic ring as its sp3 electrons drift towards the
lower energy sp2

aromatic carbon.

What we're really saying is that an sp

hybridized carbon atom is more electronegative (it's lower in energy and the electrons prefer to
move towards it) than an sp2 hybridized carbon atom, which in turn is more electronegative than
an sp3

hybridized carbon atom.

Answer

Look at the figure below, notice that in the alkyl carbocation on the left the cationic center is
attached to an sp3 carbon, whereas in the vinylic cation in the middle, the cationic center is
attached to a more electronegative sp2. carbon. For a positive center to be attached to a more
electronegative group is destabilizing. Hence the vinylic cation is less stable than a typical alkyl
cation.

Things are even worse with the aryl carbocation on the right. Here the positive carbon is attached
to 2 sp2 carbons. Destabilizing the aryl cation even further is its geometry. A vinyl cation prefers
to be linear, but due to geometrical constraints imposed by the aromatic ring the aryl cation must
be bent and the empty orbital is forced to be sp2 rather than p

. These three factors combine to make the aryl carbocation even higher in energy than the vinyl
cation.

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edited Sep 30 '15 at 22:40
answered May 7 '14 at 16:20

ron
63.5k8114214

I was taught that electrons from an sp3 carbon move to an sp2 carbon due to
hyperconjugation, that is: the shift of a bonded electron into the unhybridised p orbital of the sp2
carbon. Is the shift of electrons due to a combination of both this and inductive effect? –
Tinkidinki Feb 20 '16 at 1:55
1
Yes, that's how I see it, a mix of resonance and inductive effects. – ron Feb 20 '16 at 3:58