Boroxines are the six-membered cydotrimeric dehydration products of organoboronic acids, 3R-B(OH)(2) R3B3O3 + 3H(2)O, and in recent years have emerged as a useful class of organoboron molecules with applications in organic synthesis both as reagents and catalysts, as structural components in boronic-acid-derived pharmaceutical agents, and as anion acceptors and electrolyte additives for battery materials [Korich, A. L.; Iovine, P. M. Dalton Trans. 2010, 39, 1423 1431]. Second-order Moller-Plesset perturbation theory, in conjunction with the Dunning-Woon correlation-consistent cc-pVDZ, aug-cc-pVDZ, cc-pVTZ, and aug-cc-pVTZ basis sets, was used to investigate the structures and relative energies of the endo-exo, anti, and syn conformers of the aliphatic boronic acids R B(OH)(2) (R = H, H3C, H2N, HO, and F), as well as the thermodynamics of their boroxine formation; single-point calculations at the MP2/aug-cc-pVQZ, MP2/aug-cc-pV5Z, and CCSD(T)/aug-cc-pVTZ levels using the MP2/aug-cc-pVTZ optimized geometries were also performed in selected cases. The endo-exo conformer was generally lowest in energy in vacuo, as well as in PCM and CPCM models of aqueous and carbon tetrachloride media. The values of Delta H-298(0) for boroxine formation via dehydration from the endo-exo conformers of these aliphatic boronic acids ranged from -2.9 for (H2N)(3)B3O3 to +12.2 kcal/mol for H3B3O3 at the MP2/aug-cc-pVTZ level in vacuo; for H3B3O3, the corresponding values in PCM/UFF implicit carbon tetrachloride and aqueous media were +11.2 and +9.8 kcal/mol, respectively. On the basis of our calculations, we recommend that Delta H-f(298 K) for boroxine listed in the JANAF compilation needs to be revised from -290.0 to approximately -277.0 kcal/mol.