Photoelectron Spectroscopic Study of Skew Compounds. Methylhydrazine and Unsymmetrical Dimethylhydrazine

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Abstract
The He I photoelectron spectra of unsymmetric hydrazines CH3HNNH2 and (CH3)2NNH2 have been measured and CNDO/2calculations have been carried out, in which gauche (outer- and inner-skew) forms and trans form were taken into account for CH3HNNH2. It has been found that nonbonding splittings in the photoelectron spectra are well reproduced by CNDO/2 calculations with gauch forms. The present result of conformation are supported by available conformational studies. The following conclusions have been obtained on orbital assignments of the photoelectron spectra: 1) The first and second bands are due to the methylated and unmethylated nitrogen lone pairs, respectively. 2) The third bands are attributed to the N–N bonding orbitals. 3) The rest of the photoelectron spectra up to 18 eV can be explained in terms of other p-type orbitals (C–N bonding, CH3 pseudo π, and NH2 pseudo π).