Synthesis and structure of novel perfluorinated iodinanes

Several novel iodinanes have been prepared and structurally characterized. The structures of all are heavily influenced by secondary bonding involving the iodine(III) center and oxygen or chlorine. The iodonium salt, [Ph(CF3C H2)I]CF3SO2NSO2CF3, has a chain structure with the anion in a transoid conf ormation, while the diphenyl derivative, [Ph2I]CF3SO2NSO2CF3, forms a dimer ic structure which stabilizes a cisoid conformation of the anion. In compar ison to the known compound, PhICl2, which has a simple chain structure, per fluoroalkyliodinedichlorides CF3CH2ICl2 and CHF2(CF2)(5)CH2ICl2, have more complicated structures in which weak interactions between chains, coupled w ith aggregation of perfluoro groups, results in the formation of layers. Th e dicarboxylate, CF3CH2T(O2CCF3)(2) has a T-shaped coordination similar to other derivatives, but forms a tetrameric array of molecules not previously seen. (C) 2000 Elsevier Science B.V. All rights reserved.