A carbocation is a positively charged species. The positive
charge is localised on an sp2
hybridised carbon atom. Hence the carbocation itself is planar
around this carbon. The p orbital of the sp2 carbon
is empty. Typically they are significantly stabilised if the positive
charge can be delocalised across the molecule, and thus they form
a part of our discussion of resonance.
As already noted, alkyl groups donate electron density, and hence
the more of these groups surrounding the sp2 carbon,
the more stable it will be.
This helps us to explain Markownikow's rule in more detail; it
is actually just a disguised way of saying the most stable carbocation
forms preferentially.
There are other ways to stabilise carbocations, for example, we
can use the empty p orbital to spread the charge:

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In this case, the empty p orbital (indicated
with a "+") is next to a pi bond, and can overlap
with the p orbitals nearest it, thus spreading the positive
charge over the whole of the molecule, which increases the
stability. This case is an example of an allylic
carbocation. This concept is closely linked to
resonance, which we will look at in more detail later. |
We can extend the concept above further, and spread
the charge into a benzene ring in the same manner.
A curious example of an unlikely looking stabilised
carbocation is:
This seven membered ring is actually aromatic, which
is where it achieves its surprising stability.
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