Experimental and Quantum Mechanical Study of Nucleophilic Substitution Reactions of meta- and para-Substituted Benzyl Bromides with Benzylamine in Methanol: Synergy Between Experiment and Theory

Abstract

This work involves the experimental and theoretical study of the nucleophilic substitution of meta- and para-substituted benzyl bromides with benzylamine. Conductometric rate experiments confirm the applicability of the Hammett linear free-energy relationship to this system. To gain a deep understanding of the physical chemistry at play, a quantum mechanical study of the reaction is also conducted. The quantum mechanical calculations not only reproduce the experimental free energy of activation, but also provide greater insights at the molecular and atomic level. Isolation of the calculated transition state structure and application of the Hammett equation to its electronic, structural, and energetic properties are studied.