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Self-Assembly of Hydroxy(phenyl)iodonium Ions in Acidic Aqueous Solution: Preparation, and X-ray Crystal Structures of Oligomeric Phenyliodine(III) Sulfates

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posted on 01.06.2009, 00:00 by Victor N. Nemykin, Alexey Y. Koposov, Brian C. Netzel, Mekhman S. Yusubov, Viktor V. Zhdankin
The treatment of [(diacetoxy)iodo]benzene with sodium bisulfate leads to the formation of oligomeric cationic species resulting from self-assembly of hydroxy(phenyl)iodonium ions, [PhIOH]+, in an aqueous acidic media. Depending on the PhI(OAc)2:NaHSO4 ratio, three new oligomeric products have been isolated and characterized by X-ray crystallography. The treatment of 5 equiv of PhI(OAc)2 with 1 equiv of NaHSO4·H2O affords the previously unknown μ-oxo-[bis(acetoxy)iodo]benzene, PhI(OAc)OI(OAc)Ph, which was structurally characterized by X-ray crystallography. In the solid-state, this μ-oxo product forms an isolated diamond-core dimeric structure with pentagonal-planar iodine centers. The interaction of PhI(OAc)2 with 1 equiv of NaHSO4·H2O affords a solid-state polymeric phenyliodine(III) sulfate, [(PhIO)3·SO3]n, in which bis(μ-oxo)triiodanyl dication repeat units are linked by sulfate anions. Three of these neighboring polymeric chains form pseudo triple-helix supramolecular structure, which translates along crystallographic b-axis. The reaction of PhI(OAc)2 with 3 equiv of NaHSO4·H2O results in the formation of a tetrameric phenyliodine(III) sulfate, PhI(OH)OSO2O(Ph)IOI(Ph)OSO2OI(OH)Ph, the solid state structure of which consists of μ-oxodiiodanyl dicationic species linked by sulfate anions to the terminal hydroxy(phenyl)iodonium groups. The pseudo double-helix structure of this compound formed by the strong intermolecular interactions between two neighbor μ-oxodiiodanyl dicationic fragments and four (per pseudo helix dimer) areas of sulfate anions to the terminal hydroxy(phenyl)iodonium groups interactions.