The iodonium pseudohalide compounds, [(C6F5)2I][X] (X = SCN and CN), were synthesized by means of fluoride substitution in [(C6F5)2I][F] with the Lewis acidic reagents (CH3)3Si-NCS and (CH3)3Si-CN. Both iodonium pseudohalides are intrinsically unstable solids. Decomposition resulted in equivalent amounts of C6F5I and C6F5SCN or C6F5I and C6F5CN, respectively. In case of [(C6F5)2I][SCN] single crystals could be grown from CH2Cl2. The crystal structure revealed a dimeric structure with an eight-membered ring formed by two ambident anions bridging the iodine atoms of two cations by N and S coordination. The favored dimerization of [(C6F5)2I][SCN] and [(C6F5)2I][CN] in the gas phase is supported by ab initio computations. A comparison of the iodonium pseudohalides and the corresponding pentafluorophenylxenonium pseudohalides will be discussed.

Interaction of the electrophilic bis(pentafluorophenyl)iodonium cation, [(C6F5)2I]+, and the related pentafluorophenylxenonium cation, [C6F5Xe]+, with the ambident pseudohalogenide anions [SCN]� and [CN]�

248th National Meeting (2014)

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