Factors determining tautomeric equilibria in Schiff bases

Schiff bases derived from o-hydroxyaldehydes present keto and enol tautomeric forms; the relative equilibrium between these two tautomers depending on the particular aldehyde the Schiff bases is derived from. Thus benzaldehyde produces a stable enol tautomer, while a naphthaldehyde produces a mixture of keto and enol tautomers. The energy difference between these tautomers is very small (∼5 kJ/mol) and therefore close to current precision limits of ab initio and DFT based quantum calculations. NMR spectroscopy results, which allows for the determination of the stable structure when one tautomer is prevalent, can be very difficult to interpret when both tautomers are present. We calculate energy differences between the tautomers and demonstrate that the precision of current DFT calculations is not sufficient to predict the most stable structure. On the other hand, DFT calculations of the NMR chemical shifts (using the GIAO technique) can properly interpret the spectroscopy results allowing the characterization of the experimentally present tautomers and the estimation of the relative abundance of each when both are present.