In solution, are the hydrogen bonds in monoprotonated N,N,N',N'-tetramethyl-1,8-naphthalenediamines single- or double-well? To answer this question, isotopic perturbation of equilibrium is applied to a mixture of -d(0), -d(3), -d(6), -d(9), and -d(12) isotopologs. The N-methyls of the 2,7-dimethoxy analogue show intrinsic isotope shifts from the geminal CD(3) and from only one distant CD(3), an unusual stereochemical effect transmitted across the hydrogen bond. The (13)C NMR splittings and intensities at the various ring carbons of both ions are consistent with perturbation isotope shifts, intrinsic shifts, or a combination of both. The perturbation shifts mean that the protons reside in a double-minimum potential and that each ion is a pair of rapidly interconverting tautomers. The significance of this result for the role of low-barrier hydrogen bonds in enzyme-catalyzed reactions is discussed.
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