A molecular mechanism of the [3+2] cycloaddition has been explored using various DFT theoretical levels. It was found that the reaction proceeds via transition states with different synchronicity, but no intervention of the theoretical possible zwitterionic intermediates. Additionally, regioselectivity of the cycloaddition process has been analysed using vibrational analysis of localised TSs

With the focus on calculating the equilibrium constant (Ka) of arsonic acids (RAsO(OH)2) in aqueous media, the behavior of both neutral and negatively charged species of some arsonic acids have been considered through the isodesmic reaction scheme with polarized continuum model of solvation. The relative pKa values of a number of arsonic acids were calculated using density functional theory (DFT), with methylarsonic acid (CH3AsO(OH)2) used as a reference molecule. Various basis sets such as (6-31G(d), 6-31+G(d), 6-311++G(d,p) and 6-311++G(2d,2p)) in conjunction with B3LYP computational method were examined. Finally the latter one was found to give better results. The results of applied B3LYP 6-311++G(2d,2p) method for pKa values of 25 arsonic acids in aqueous media showed good agreement with corresponding experimental pKa values. In this level of theory the average error was less than 0.3 pKa units. The type of substituent affected the acid strength, with electron withdrawing substituents lowering the pKa and electron releasing groups increasing it.