Computational study of the gas phase reaction of hydrogen azide and corannulene: A DFT study

Abstract

The present computational study aims to better understand the nature of the gas phase reaction mechanism of corannulene and hydrogen azide molecules using MP2/6-311+G(d,p)//B3LYP/6- 31+G(d) level of theory. The reactions of hydrogen azide with various kinds of C–C bond of corannulene in eleven pathways were considered. Vibrational analysis and intrinsic reaction coordinate (IRC) calculations were done and the rate constants for all paths were calculated by using canonical transition state theory (CTST). Results showed that rim position and after that hub position are the best for functionalization of corannulene with hydrazoic acid molecule, energetically and the major products are corannulene with an aziridine group in rim and hub positions, respectively. Addition of HN3 to flank and spoke positions of corannulene and 1,4- addition of HN3 are endothermic in all investigated pathways. For flank position, only a triazoline intermediate is produced and elimination of N2 or other pathways dos not proceed.