Electrophilic Aromatic Substitution
Structure of a Sigma Complex


Electrophilic aromatic substitution is the most important reaction mechanism for the functionalization of benzene. Chlorination is a typical example. Here, the electrophile Cl+ approaches benzene and forms a "sigma complex". A C-Cl sigma bond is formed using two of the pi-electrons and the positive charge is dispersed over the remaining five CH groups in the ring.


Figure. The MP2(full)/6-31G* optimized structure of the sigma complex formed in the chlorination of benzene.