Tautomerism in Five-membered Nitrogen Heterocycles. A Test of the Reliability of Semiempirical (AMI, PM3, MNDO) Quantum Chemical Methods

Abstract

Abstract The reliability of three popular semiempirical quantum chemical methods (AM1, PM3, MNDO) for the treatment of tautomeric equilibria is tested in a series of five-membered nitrogen heterocycles. The known flaw of MNDO to overestimate the stability of compounds with two or more adjacent pyridine-like lone pairs is also present in AM1 and to a somewhat lesser extent in PM3. Tautomeric species differing in the number of adjacent pyridine-like lone pairs, thus, cannot be adequately treated by these semiempirical methods. Both AM1 as well as PM3, however, represent major improvements over MNDO in the case of lactam-lactim tautomerism. The stability of N-oxides as compared to N-hydroxy tautomers seems to be overestimated by the PM3 method. All three semiempirical methods yield quite reliable ionization potentials and dipole moments.