The enols of 4-cyano-2,2,6,6-tetramethyl-3,5-heptanedione and of nitromalonamide were prepared as statistical mixtures of 18On (n = 0,1,2) isotopologues. The symmetries of their hydrogen bonds were probed by isotopic perturbation of their 13CO NMR signals. The former mixture shows a total of four signals, due to both intrinsic and perturbation isotope shifts. Therefore that enol is a mixture of tautomers with an asymmetric hydrogen bond. In contrast, the mixture of isotopologues of nitromalonamide enol shows only two signals, due solely to an intrinsic isotope shift. Therefore this is the first case, to be compared with FHF anion, of a neutral species with a single symmetric structure in solution, and with a centered hydrogen.

Symmetry of the hydrogen bonds of two enols in solution

2019 Fall National Meeting

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