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

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, [PhlOH](+), in an aqueous acidic media. Depending on the Phl(OAc)(2):NaHSO(4) ratio, three new oligomeric products have been isolated and characterized by X-ray crystallography. The treatment of 5 equiv of Phl(OAc)(2) with 1 equiv of NaHSO(4)center dot H(2)O affords the previously unknown mu-oxo-[bis(acetoxy)iodo]benzene, Phl(OAc)Ol(OAc)Ph, which was structurally characterized by X-ray crystallography. In the solid-state, this mu-oxo product forms an isolated diamond-core dimeric structure with pentagonal-planar iodine centers. The interaction of Phl(OAc)(2) with 1 equiv of NaHSO(4)center dot H(2)O affords a solid-state polymeric phenyliodine(III) sulfate, [(PhlO)(3)center dot SO(3)](n), in which bis(mu-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 Phl(OAc)(2) with 3 equiv of NaHSO(4)center dot H(2)O results in the formation of a tetrameric phenyliodine(III) sulfate, Phl(OH)OSO(2)O(Ph)IOI(Ph)OSO(2)Ol(OH)Ph, the solid state structure of which consists of mu-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 mu-oxodiiodanyl dicationic fragments and four (per pseudo helix dimer) areas of sulfate anions to the terminal hydroxy(phenyl)iodonium groups interactions.