n–π Electron donor–acceptor complexes. II. Aliphatic amines with dinitrobenzenes

Abstract

The interaction of several aliphatic amines as n-donors and dinitrobenzenes (DNB) as π-acceptors has been studied in n-hexane. The formation of electron donor – acceptor (EDA) complexes is proposed to explain the spectroscopic behaviour of the mixtures. The stability constants (Ks) for these complexes have been calculated by an iterative procedure. For a given acceptor, the donor strength of RNH2 > R2NH > R3N was found. This order is explained by considering the role that steric effect may play in the EDA complex formation. On the other hand, the fact that for a given donor Ks follows the order 1,2-DNB > 1,3-DNB > 1,4-DNB, and that 1,2-DNB reacts with primary amines, led to the proposal of orientational complexes. These EDA complexes may be considered intermediates in aromatic nucleophilic substitution reactions.