2,7-Disubstituted proton sponges as borderline systems for investigating barrier-free intramolecular hydrogen bonds. Protonated 2,7-bis(trimethylsilyl)- and 2,7-di(hydroxymethyl)-1,8-bis(dimethylamino)naphthalenes

Protonated 2,7-bis(trimethylsilyl)- and 2,7-di(hydroxymethyl)-1,8-bis(dimethylamino)naphthalenes have been prepared and studied by a combination of X-ray crystallography at room and low temperatures, IR and NMR spectroscopic techniques in conjunction with quantum-chemical calculations. It was demonstrated that the intramolecular [NHN]+ hydrogen bond in the 2,7-bis(trimethylsilyl) system, being sterically compressed, is the shortest among all known aromatic diamine systems. Nevertheless, as it is evidenced by the primary 1H/2H isotope effect, IR spectra and MP2 calculations, a double minimum potential for the proton motion still exists with a very low barrier estimated to be about 0.7 kcal/mol. An influence of a counter-anion on the NH proton involving the spatially hindered H-bond is also considered.

Graphical abstractThe experimental evidence of the shortest [NHN]+ but yet asymmetric intramolecular hydrogen bond among all known aromatic diamine systems is reported, supported by IR, NMR and theoretical calculations of this and related cation with ortho-CH2OH groups.Figure optionsDownload full-size imageDownload as PowerPoint slide