The relationships between direct substituents, aromaticity and kinetic stability of pentazole ring

Abstract

The two directly substituted pentazoles, N₅NH₂ and N₅COOH, were designed to theoretically study the relationships between substituents, aromaticity and kinetic stability thereof. Analysis shows their kinetic stability order described by the energy separations between the highest occupied molecule orbital (HOMO) and the lowest unoccupied molecule orbital (LUMO), viz. HOMO-LUMO gap, is line with the aromaticity orders obtained from nucleus-independent chemical shift (NICS), harmonic oscillator measure of aromaticity (HOMA), Bird aromaticity index (I) and isochemical shielding surface (ICSS), which is N₅NH₂ > N₅COOH. But this order is contrary to the heat stability order according to Ref [1] The inconsistency between heat stability and kinetic stability reveals the fact that stability of compounds is a complex character and different according to the compound property of the study. The consistency of kinetic stability order with the aromaticity orders described by NICS, NICSS_ZZ, HOMA, I and ICSS indicates these widely accepted methods for aromaticity estimating are reliable for the two given compounds. As for the effect on aromaticity of pentazole ring from substituent, electron-donating substituent have stronger effect than electron-withdrawing substituent.