Isomers and conformers of two push–pull hydrazines studied by NMR and vibrational spectroscopy and by ab initio calculations

The isomers and conformers of two push–pull hydrazines: 3-N,N-dimethylhydrazino-2-acetyl propenenitrile [(H3C)2NNHCHC(CN)(COCH3)] (DMHAP) and 3-N,N-dimethylhydrazino-2-methylsulfonyl propenenitrile [(H3C)2NNHCHC(CN)(SO2CH3)] (DMHSP) have been studied experimentally by NMR and vibrational spectroscopy and theoretically by the ab initio calculations at MP2 level in 6-31G** basis set. The IR and Raman spectra of both compounds as a solid and solute in various solvents have been recorded. The NMR spectra were obtained in chloroform and DMSO at room temperature.Both compounds have been prepared by the same way. NMR spectra revealed that DMHAP was prepared as a pure Z-isomer whereas in the case of DMHSP a pure E-isomer was obtained. Due to the low barrier for both compounds practically free isomerisation process occurred in the solutions but in opposite directions. Whereas DMHAP exists in the solid state and in the less polar solvent as Z-isomer, in more polar solvents the appearance of next two conformers of E-isomer was observed. On the contrary DMHSP exists in the solid state and in the more polar solvent as E-isomer only but in less polar solvent the presence of Z-isomer was observed as well.Conformational possibilities of both studied compounds are given by the rotation of dimethylhydrazino group with its anti- or syn-orientation towards the olefinic double bond. Moreover, by the rotation of the acetyl group with Z- and E-orientation of carbonyl bond towards olefinic double bond can occur in DMHAP. Vibrational and NMR spectra revealed the existence of single conformer with intramolecular hydrogen bond for Z-isomer in less polar solvent and next two conformers for E-isomer of DMHAP with Z-orientation of acetyl group and anti and syn orientation of dimethylhydrazine group in more polar solvents. For E-isomer of DMHSP two conformers with anti or syn orientations of dimethylhydrazino group have been also confirmed by NMR spectra in more polar solvents. Additionally the third DMHSP conformer with anti orientation of dimethylhydrazino group originating from Z-isomer was detected in less polar solvents. These experimental findings have been supported by ab initio calculations with solvent effect inclusion.