title: A rare example of a krypton difluoride coordination compound: [BrOF2][AsF6] x 2 KrF2.
abstract: The synthesis of [BrOF(2)][AsF(6)] x 2 KrF(2), its structural characterization, and bonding are described in this study. Although several KrF(2) adducts with transition metal centers have been previously reported, none have been crystallographically characterized. The solid-state Raman spectrum of [BrOF(2)][AsF(6)] x 2 KrF(2) has been assigned with the aid of quantum-chemical calculations. The low-temperature (-173 degrees C) X-ray crystal structure of [BrOF(2)][AsF(6)] x 2 KrF(2) consists of isolated molecular units and represents an example of KrF(2) coordinated to a main-group atom. The coordination geometry around the BrOF(2)(+) cation renders the free valence electron lone pair more compact than in free BrOF(2)(+). The KrF(2) ligands are coordinated trans to the fluorine atoms of BrOF(2)(+) with the AsF(6)(-) anion coordinated trans to oxygen. The quantum theory of atoms in molecules (QTAIM) and electron localization function (ELF) analyses have been carried out in order to define the nature of the bonding in the complex. A significant amount of charge (0.25 e) is transferred to BrOF(2)(+) from the two KrF(2) ligands (0.10 e each) and from the AsF(6)(-) anion (0.05 e). Significant polarization also occurs within the KrF(2) ligands, which enhances the anionic characters of the fluorine bridges. The interaction energy is mostly governed by the electrostatic interaction of the positively charged bromine atom with the surrounding fluorine atoms.
authors.affiliation: Department of Chemistry, McMaster University, Hamilton, Ontario L8S 4M1, Canada.
authors.forename: David S
authors.initials: DS
authors.lastname: Brock
authors.forename: Jonathan J Casalis
authors.initials: JJ
authors.lastname: de Pury
authors.forename: Hélène P A
authors.initials: HP
authors.lastname: Mercier
authors.forename: Gary J
authors.initials: GJ
authors.lastname: Schrobilgen
authors.forename: Bernard
authors.initials: B
authors.lastname: Silvi