Diradicalar Character and Ring Stability of Mesoionic Heterocyclic Oxazoles and Thiazoles by Ab Initio Mono and Multi-Reference Methods

Mesoionics are neutral compounds that cannot be represented by a fully covalent or purely ionic structure. Among the possible mesomeric structures of these compounds are the diradical electronic configurations. Theoretical and experimental studies indicate that some mesoionic rings are unstable, which may be related to a significant diradical character, that until then is not quantified. In this work, we investigated the diradical character of four heterocycles: 1,3-oxazol-5-one, 1,3-oxazol-5-thione, 1,3-thiazole-5-one, and 1,3-thiazole-5-thione. The oxazoles are known to be significatively less stable than thiazoles. DFT and ab initio single (B3LYP, MP2, CCSD, and QCISD) and ab initio multi-reference (MR-CISD) methods with three basis sets (6-311+G(d), aug-cc-pVDZ, and aug-cc-pVTZ) were employed to assess the diradical character of the investigated systems, in gas phase and DMSO solvent, from three criteria: (i) HOMO-LUMO energy gap, (ii) determination of energy difference between singlet and triplet wave functions, and (iii) quantification of the most significant diradical character (y0, determined in the unrestricted formalism). All of the results showed that the diradical character of the investigated systems is very small. However, the calculated electronic structures made it possible to identify the possible origin of the oxazoles instability, which can help the design of mesoionic systems with the desired properties.