Does [I<sub>3</sub>]<sup>+</sup> Act as an “[I]<sup>+</sup>” Donor to CH<sub>3</sub>CN and N<sub>2</sub>O? Structure of [H<sub>3</sub>CCN-I-NCCH<sub>3</sub>]<sup>+</sup>[AsF<sub>6</sub>]<sup>−</sup>

The solid state structure of the [(CH<sub>3</sub>CN)<sub>2</sub>I]<sup>+</sup> cation in [(CH<sub>3</sub>CN)<sub>2</sub>I][AsF<sub>6</sub>] was determined using single crystal X-ray diffraction. The highly reactive cation was prepared by reaction of [I<sub>3</sub>][AsF<sub>6</sub>] with CH<sub>3</sub>CN in liquid SO<sub>2</sub>. In the solid state, the CNI backbone consisting of seven atoms is linear and shows a dicoordinate iodine center. The ability of [I<sub>3</sub>][AsF<sub>6</sub>] to act as a source of “[I]<sup>+</sup>” to CH<sub>3</sub>CN and N<sub>2</sub>O is compared, and the computed structures of the [CH<sub>3</sub>CNI]<sup>+</sup>, [(CH<sub>3</sub>CN)<sub>2</sub>I]<sup>+</sup>, [IN<sub>2</sub>O]<sup>+</sup> and [ION<sub>2</sub>]<sup>+</sup> cations are discussed.