The dithiacyclooctane cation (DTCO+): conformational analysis, interconversion barriers and bonding

Abstract

A theoretical conformation analysis of the dithiacyclooctane radical cation (DTCO⁺) suggests that the lowest energy conformer is a chair-boat, with a partial but significant S–S σ bond. For the ring flip process of this molecule we calculate a barrier of 40 kJ mol^–1 and two possible pathways: one involves a boat-boat conformer and an untwisted transition structure, the other a chair-chair conformer and a twisted transition structure.