Electrophilic Hypervalent Trifluoromethylthio-Iodine(III) Reagent.

Herein we report the design and synthesis of hypervalent trifluoromethylthio-iodine(III) reagent and the elucidation of its structure by NMR spectroscopy and X-ray crystallography. The trifluoromethylthiolation reactions of with various nucleophiles were explored, and this compound was found to be a versatile electrophilic reagent for the transfer of a trifluoromethylthio group (-SCF). The hydrogen-bonding mode responsible for the activation of by the solvent 1,1,1,3,3,3-hexafluoro-2-propanol was investigated both experimentally and computationally.