Compensation and cooperative effects in H-bond thermodynamics of hydroperoxides

Self-association of cumyl (CUH), tertiary butyl and 3-phenylmethyl hydroperoxides in various solvents and hetero-association of CUH with acetone and acetophenone in n-decane solutions were studied by FTIR spectroscopy. The obtained results were analyzed in combination with DFT data on linear and cyclic CUH self-associates. The analysis of the complexation enthalpies and entropies revealed compensation and cooperative effects, which were for the first time observed for H-bonding of hydroperoxides.