title: Anion-π interactions in salts with polyhalide anions: trapping of I4(2-).
abstract: The directionality of interaction of electron-deficient π systems with spherical anions (e.g,. halides) can be controlled by secondary effects like NH or CH hydrogen bonding. In this study a series of pentafluorophenyl-substituted salts with polyhalide anions is investigated. The compounds are obtained by aerobic oxidation of the corresponding halide upon crystallization. Solid-state structures reveal that in bromide 2, directing NH-anion interactions position the bromide ion in an η(1)-type fashion over but not in the center of the aromatic ring. The same directing forces are effective in corresponding tribromide salt 3. In the crystal, the bromide ion is paneled by four electron-deficient aromatic ring systems. In addition, compounds 4 and 6, which have triiodide and the rare tetraiodide dianion as anions, are described. Computational studies reveal that the latter is highly unstable. In the present case it is stabilized by the crystal lattice, for example, by interaction with electron-deficient π systems.
authors.affiliation: Institut für Organische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Müller
authors.forename: Markus
authors.initials: M
authors.lastname: Albrecht
authors.forename: Verena
authors.initials: V
authors.lastname: Gossen
authors.forename: Tanja
authors.initials: T
authors.lastname: Peters
authors.forename: Andreas
authors.initials: A
authors.lastname: Hoffmann
authors.forename: Gerhard
authors.initials: G
authors.lastname: Raabe
authors.forename: Arto
authors.initials: A
authors.lastname: Valkonen
authors.forename: Kari
authors.initials: K
authors.lastname: Rissanen