Theoretical Study of Strong Basicity in Aromatic Diamines.

The basic strength of NH(3), NH(2)(CH(3)), NH(CH(3))(2), and N(CH(3))(3) has been evaluated by generating for each species the orbital that plays the dominant role in electron delocalization to an attached proton. The theoretically determined strength has been found to correlate well with the calculated value of proton affinity. The analysis has then been extended to a so-called "proton-sponge" compound, 1,8-bis(dimethylamino)naphthalene. The major component of the orbital of the diamine that captures the proton has been demonstrated to be an in-phase combination of two lone-pair orbitals. The out-of-phase combination elevated in energy by a strong antibonding interaction between two lone pairs of electrons is not necessarily the source of the exceptionally high basicity. The electrostatic interaction has been shown to be the major origin of stabilizing the protonated system, but the location of the captured proton is governed by electron delocalization. A similar conclusion has also been derived for 4,5-bis(dimethylamino)fluorene.