The insertion reactions of “crowned” indium(I) trifluoromethanesulfonate into carbon–chlorine bonds

Whereas the soluble reagent indium(I) trifluoromethanesulfonate, InOTf, does not appear to react rapidly with chlorinated solvents, the crown ether ligated compounds [In(18-crown-6)][OTf] and [In(dibenzo-18-crown-6)][OTf] react rapidly with CH2Cl2 and CHCl3 to produce the corresponding C–Cl insertion products. The structural features and the formation of the new indium-containing products are rationalized.