Abstract
The 35Cl n.q.r. spectra of 29 trichloroacetic acid complexes with various bases, mainly pyridines and their N-oxides, have been studied. The dependence of the average 35Cl n.q.r. frequencies, text-decoration:overlineνQ, on ΔpKa have been analysed in terms of the proton-transfer equilibrium, and the data can be explained either on the basis of a double-minimum potential function with rapid flipping of the proton between two equilibrium sites or one broad minimum. Infrared spectra of such complexes show very broad absorptions over the whole region, with numerous so-called ‘Evans holes’. Variations of the absorption in complexes from the inversion region are similar to those observed in solution. In solids the range of the inversion is shifted to the lower ΔpKa values. Nitrogen and oxygen bases show similar spectral behaviour. In the vicinity of 50% proton transfer the spectral features are similar for A—H…B and A–…HB+ complexes.
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Schedule a callMore From: Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
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