Tautomerism in the Solid State and in Solution of a Series of 6-Aminofulvene-1-aldimines

Abstract

To study systems able to sustain intramolecular proton-transfer, we have prepared a series of six aminofulvene aldimines including several labeled with (15)N and (2)H. These compounds show coupling constants through the hydrogen bond, (1h)J((15)N- (1)H) and (2h)J((15)N-(15)N). The position of the tautomeric equilibria, i.e., on what nitrogen atom is the proton, was determined in the solid state and in solution. The crystal structure of N[[5-[(phenylamino)methylene]-1,3-cyclopentadien-1-yl]methylene]pyrrole-1-amine (3) has been determined by X-ray analysis. In solution, both N-H and C-H tautomers were observed and their structures assigned by NMR spectroscopy. Particularly useful is the value of the (1)J((15)N-(1)H) coupling constant.