The Heavy Atom Structure, “cis effect” on Methyl Internal Rotation, and 14N Nuclear Quadrupole Coupling of 1‐Cyanopropene from Quantum Chemical and Microwave Spectroscopic Analysis

Abstract

AbstractThe microwave spectrum of 1‐cyanopropene (crotonitrile) was remeasured using two pulsed molecular jet Fourier transform microwave spectrometers operating from 2.0 to 40.0 GHz. The molecule exists in two isomer forms, E and Z, with respect to the orientation between the methyl and the cyano groups. The spectrum of the Z isomer is more intense. Due to internal rotation of the methyl group, doublets containing A and E torsional species were found for all rotational transitions. Hyperfine splittings arising from the 14N nuclear quadrupole coupling were resolved. The heavy atom structure of the Z isomer was determined by observation of 13C and 15N isotopologue spectra in natural abundances. The experimental results were supported by quantum chemistry. The complex spectral patterns were analyzed and fitted globally, and the barriers to methyl internal rotation are determined to be 478.325(28) cm−1 and 674.632(76) cm−1 for the Z and E isomers, respectively. The non‐bonded intramolecular electrostatic attraction between the methyl group and the 1‐cyano substituent overcomes steric hindrance, leading to higher stability of the Z isomer. The consequence is a slight opening of 3.2° of the C(1)‐C(2)‐C(3) angle and a radical decrease of the methyl torsional barrier in the Z isomer due to steric repulsion.