Density functional theory (DFT) calculations of conformational energies and interconversion pathways in 1,2,7-thiadiazepane

Abstract

The molecular structure and conformational analysis of 1,2,7-thiadiazapane conformers were investigated by density functional theory (DFT) calculations at the B3LYP/cc-pVDZ level of theory. Four twist-chair (TC), six twist-boat (TB), two boat (B), two chair (C) and four twist (T) conformers were identified as minima and transition states for 1,2,7-thiadiazepane. The TC1 conformer is the most stable conformer and the twist-chair conformers are predicted to be lower in energy than their corresponding boat and chair conformations. DFT predicts a small barrier to pseudo-rotation and a remarkable activation barrier for the conformational interconversion of the twist-chair conformers to their corresponding boat conformers. The simplest conformational process and the one with the lowest barrier is the degenerate interconversion of the twist-chair 3 (TC3) conformation with itself via the CS symmetric chair (C2) transition state. The calculated strain energy barrier for this process is 2.41 kJ mol-1. The highest conformational interconversion barrier is between TC2 and twist-boat 3 (TB3) forms, which was found to be 75.62 kJ mol-1.