title: Self-assembly of hydroxy(phenyl)iodonium ions in acidic aqueous solution: preparation, and X-ray crystal structures of oligomeric phenyliodine(III) sulfates.
abstract: 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):NaHSO(4) 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 NaHSO(4).H(2)O affords the previously unknown mu-oxo-[bis(acetoxy)iodo]benzene, PhI(OAc)OI(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 PhI(OAc)(2) with 1 equiv of NaHSO(4).H(2)O affords a solid-state polymeric phenyliodine(III) sulfate, [(PhIO)(3).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 PhI(OAc)(2) with 3 equiv of NaHSO(4).H(2)O results in the formation of a tetrameric phenyliodine(III) sulfate, PhI(OH)OSO(2)O(Ph)IOI(Ph)OSO(2)OI(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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Minnesota Duluth, 1039 University Drive, Duluth, Minnesota 55812, USA. vnemykin@d.umn.edu
authors.forename: Victor N
authors.initials: VN
authors.lastname: Nemykin
authors.forename: Alexey Y
authors.initials: AY
authors.lastname: Koposov
authors.forename: Brian C
authors.initials: BC
authors.lastname: Netzel
authors.forename: Mekhman S
authors.initials: MS
authors.lastname: Yusubov
authors.forename: Viktor V
authors.initials: VV
authors.lastname: Zhdankin
mesh_terms: D018360:Crystallography, X-Ray; D006863:Hydrogen-Ion Concentration; D007477:Ions / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009861:Onium Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012996:Solutions; D013463:Sulfuric Acid Esters / Q000138:chemical synthesis* / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D007477:Ions; D009861:Onium Compounds; D012996:Solutions; D013463:Sulfuric Acid Esters; D014867:Water