Computational investigation of the substituent effect in the [2 + 4] Diels–Alder cycloaddition reactions of HSi≡Si(para‐C₆H₄X) with benzene

Abstract

In this paper, the DFT method was applied at the B3LYP/6-311+G (d,p) level of theory to investigate the [2 + 4] Diels−Alder cycloaddition reactions of HSi≡Si(para-C 6 H 4 X); X = NH 2 , OH, Me, H, F, CCH, OCF 3 with benzene. It was attempted to show how the substituent affects the barrier height and thermodynamic parameters of these reactions. To illustrate the interaction between two fragments at transition states Activation Strain Model (ASM) and Energy Decomposition Analysis (EDA) were utilized. The Wiberg bond indices were used to check the progress of the reactions. The rate constant of the reaction was computed at 300 K, in the gas phase. Also, the synchronicity values of this reaction were determined. K E Y W O R D S rhenabenzyne, phosphine ligand, natural bond analysis (NBO), Tolman cone angles, Tolman's electronic parameter (TEP), para-delocalization index (PDI)