Does [I₃]⁺ Act as an “[I]⁺” Donor to CH₃CN and N₂O? Structure of [H₃CCN-I-NCCH₃]⁺[AsF₆]⁻

The solid state structure of the [(CH₃CN)₂I]⁺ cation in [(CH₃CN)₂I][AsF₆] was determined using single crystal X-ray diffraction. The highly reactive cation was prepared by reaction of [I₃][AsF₆] with CH₃CN in liquid SO₂. In the solid state, the CNI backbone consisting of seven atoms is linear and shows a dicoordinate iodine center. The ability of [I₃][AsF₆] to act as a source of “[I]⁺” to CH₃CN and N₂O is compared, and the computed structures of the [CH₃CNI]⁺, [(CH₃CN)₂I]⁺, [IN₂O]⁺ and [ION₂]⁺ cations are discussed.