Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON K1N 6N5, Canada.
Molecules. 2023 May 30;28(11):4431. doi: 10.3390/molecules28114431.
Ion-molecule reactions between the neutral ethyl- (EF), isopropyl- (IF), t-butyl- (TF) and phenyl formate (PF) and proton-bound water clusters WH and WH (W = HO) showed that the major reaction product is water loss from the initial encounter complex, followed ultimately by the formation of the protonated formate. Collision-induced dissociation breakdown curves of the formate-water complexes were obtained as a function of collision energy and modeled to extract relative activation energies for the observed channels. Density functional theory calculations (B3LYP/6-311+G(d,p)) of the water loss reactions were consistent with reactions having no reverse energy barrier in each case. Overall, the results indicate that the interaction of formates with atmospheric water can form stable encounter complexes that will dissociate by sequential water loss to form protonated formates.
中性乙基（EF）、异丙基（IF）、叔丁基（TF）和苯甲酸盐（PF）与质子结合水团 WH 和 WH（W = HO）之间的离子-分子反应表明，主要反应产物是初始碰撞复合物中失去水，最终形成质子化的甲酸盐。作为碰撞能函数获得了甲酸盐-水复合物的碰撞诱导解离分解曲线，并对其进行了建模以提取观察到的通道的相对活化能。水损失反应的密度泛函理论计算（B3LYP/6-311+G（dp））在每种情况下都与没有反向能垒的反应一致。总体而言，结果表明，甲酸盐与大气水的相互作用可以形成稳定的遭遇复合物，这些复合物将通过连续失去水形成质子化的甲酸盐而解离。
