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.