Stable Spirocyclic Meisenheimer Complexes

Meisenheimer complexes are important intermediates in Nucleophilic Aromatic Substitution Reactions (S(N)Ar). They are formed by the addition of electron rich species to polynitro aromatic compounds or aromatic compounds with strong electron withdrawing groups. It is possible to distinguish two types of Meisenheimer or σ-complexes, the σ(H)-complex or σ(X)-complex (also named ipso), depending on the aromatic ring position attacked by the nucleophile (a non-substituted or substituted one, respectively). Special examples of σ(X)- or ipso-complexes are formed through intermediate spiro adducts, via intramolecular S(N)Ar. Some of these spirocyclic Meisenheimer complexes, a type of σ(X)-complex, are exceptionally stable in solution and/or as solids. They can be isolated and characterized using X-ray, and various spectroscopic techniques such as NMR, UV-Vis, IR, and fluorescence. A few of these stable spirocyclic Meisenheimer complexes are zwitterionic and exhibit interesting photophysical and redox properties. We will review recent advances, synthesis and potential applications of these stable spirocyclic Meisenheimer complexes.