title: Halogen impact into new oxonium benzo-crown ether complexes with tetrachloro- and tetrabromoaurates(III).
abstract: Five oxonium tetrahalogenaurate(III) (Hal = Cl, Br) benzo-crown ether (BCE) complexes are prepared and reported. The new compounds are [(H3O)(B18C6)(0.58)(4'-Cl-B18C6)0.42][AuCl4] 1, [(H3O)(B18C6)][AuCl4] 2, [(H3O)(4'-Br-B18C6)][AuCl4] 3, [(H3O)(4'-Br-B18C6)][AuBr4] 4, and [(H3O)(B18C6)][AuBr4] 5. The reaction medium, distinctive from the previously used aqua regia, allowed avoiding the unwanted nitration of initial macrocycles. The compositions and structures for 1, 3, 4, and 5 were proved by single crystal X-ray crystallography. The complete conversion of tetrachloroaurate(III) to the tetrabromoaurate(III) salts resulted in complex 4 isomorphous and isostructural to 3. All compounds form the laminated structures with alternation of cationic and anionic layers. The robustness of the anionic sheets is sustained by the halogen-halogen interactions and makes crucial impact on extraction of stoichiometric products in the case of tetrabromoaurate(III) salts.
authors.affiliation: A.V. Bogatsky Physico-Chemical Institute of National Academy of Sciences of Ukraine, Lustdorfskaya doroga 86, 65080, Odessa, Ukraine.
authors.forename: Sergei M
authors.initials: SM
authors.lastname: Pluzhnik-Gladyr
authors.forename: Victor Ch
authors.initials: VCh
authors.lastname: Kravtsov
authors.forename: Marina S
authors.initials: MS
authors.lastname: Fonari
authors.forename: Gerbert L
authors.initials: GL
authors.lastname: Kamalov