Density functional theory (DFT) calculations were performed at the M06-2X level of theory to substantiate the experimental observations and detail the mechanistic pathway further. [17] The key intermediates and transition states are depicted in Figure . Initial coordination of xanthate 2d to the iodine gives intermediate I (-3.3 kcal/mol), followed by a concerted SNAr via transition state TS1 (22.2 kcal/mol) to deliver iodine(III) intermediate II. From intermediate II, the mechanism could proceed via an ene type elimination assisted by the fluoride or via nucleophilic attack of the fluoride onto the xanthate carbon.