The influence of the entropy on the proton transfer equilibria AH···B [Formula: see text]A···H+B in the dimethylphosphinic acid (DMP)-N-base and in the methanesulfonic acid (MSA)-N-oxide hydrogen bonds is studied by 1H NMR spectroscopy as a function of the ΔpKa, i.e., the pKa of the base minus the pKa of the acid. It is shown that with increasing ΔpKa the proton transfers to the N-oxide acceptor. In the DMP + N-base family of systems, first the double-minimum proton potentials (ΔH = 0) occurs and only with further increasing ΔpKa do the POH···N [Formula: see text] PO···H+N equilibria become symmetrical (ΔG = 0). ΔG and ΔH are connected by the GibbsHelmholtz equation, ΔG = ΔH TΔS. Hence, the reason of this effect is the large negative interaction entropy term (ΔSI) arising from the large order around the polar structure, which shifts the equilibria strongly to the left-hand side. With the MSA-N-oxide hydrogen bonds a single-minimum proton potential was found. The minimum shifts with increasing ΔpKa from the donor to the acceptor of the O···H+···N hydrogen bonds. It is shown that with increasing ΔpKa the proton potential becomes on average symmetrical, whereas the proton is still largely on the left-hand side. This result is also explained by the large negative interaction entropy due to the order of the environment if the proton is at the acceptor B.Key words: entropy, hydrogen bonds, infrared, spectroscopy, proton transfer.
Crystal structure of dimethylphosphinic acid anhydride, [(CH3)2P(O)]2O
