Title

Gas-Phase Nuclear Magnetic Resonance Study of Internal Isomerization in Perfluoro-2-Azapropene: Comparison of Experimental and Computed Kinetic Parameters

Document Type

Article

Publication Date

10-15-2017

Abstract

Rate constants obtained from total line-shape analysis of five temperature-dependent gas-phase NMR spectra of perfluoroazapropene yielded the kinetic barrier to internal isomerization: G298 = 66.9 (0.4) kJ mol−1. Five temperature-dependent liquid spectra (5 mol% in CDCl3) yielded G298 = 67.4 (0.8) kJ mol−1. Ab initio calculations performed using the compound methods Complete Basis Set (CBS-4M, QB3, APNO), Gaussian (G1-4), and Weizmann (W1U, WBD) gave results consistent with a transition state corresponding to nitrogen inversion. The values that best matched the experimental G298 value for each compound method were 63.9 kJ mol−1 (CBS-APNO), 66.1 kJ mol−1 (G2), and 65.6 kJ mol−1 (W1BD).