Effect of substituent on the rate of reaction between 4Y-ArNH₂, (YH, F, CI, CH₃, OCH₃, NH₂, N(CH₃)₂, CF₃, CN, NO₂) with CH₃OO• in the gas phase

Abstract

Effect of substituent (Y), including halogen (Fand CT), electron donating (ED) and electron withdrawing (EW) group on the thermoparameters and kinetic behavior of reactions between 4Y-ArNH₂; and CH₃COO• was computationally stadied using density functional theory (DFT) at M05-2X/6-311++G(d,p) method in combination with the transition state theory (TST) in Eyringpy program. Based on the three mechanisms of reaction between 4Y-ArNH₂; and CH₃COO•, namely the hydrogen transfer (HAT/PCET), single electron transfer proton transfer (SET-PT), and sequential proton los electron transfer (SPLET), the effects on the thermoparameters involved in these mechanisms were investigated. ED group reduces the bond dissociation energy (BDE) and ionization energy (IE) then also increases the rate of hydrogen transfer reaction of 4Y-ArNH₂; and CH₃COO•. Hydrogen atom transfer reaction of ArNH₂; with CH₃OO at 298.15 K in the gas phase preferably takes place no PCET with the tale constant key of 1.19-10⁻¹⁹ cm³ molecules⁻¹, s⁻¹ higher than that of kHAT of 2.19-10⁻²⁰ cm³ molecules⁻¹, s⁻¹. The rate constants of all 4Y-ArNH₂; CH₃COO• reactions were als reported and PCET mechanisen is dominated with the branching ratio (1%) ranging from 73% to 95% group.