Reactivity of propargylamines in complexation and polymerization reactions

Factors were determined which promote the formation of charge-transfer complexes of propargylamines with organic electron acceptors and a change of the activity of the triple bond in propargylamines under the effect of donor-acceptor interactions. On the basis of data from PMR spectroscopy and quantum-chemical calculations it was shown that the tendency of propargylamines to form charge-transfer complexes depends on the electron-donor properties of the substituents at the nitrogen atom. The values of the effective charges at the atoms and an analysis of the structure of the highest occupied molecular orbitals in the propargylamines and their radical cations indicate that mainly electrons localized on nitrogen atoms participate in the complexation reaction. An increase of the reactivity of the triple bond is related to an increase in its polarity under the effect of complexation.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 5, pp. 597–601, September–October, 1989.