title: [((Cl)Im(Dipp))P=P(Dipp)][GaCl4]: a polarized, cationic diphosphene.
abstract: The reaction of the neutral diphosphanide [((Cl)Im(Dipp))P-P(Cl)(Dipp)] (6) ((Cl)Im(Dipp) = 4,5-dichloro-1,3-bis(Dipp)-imidazol-2-yl; Dipp = 2,6-di-iso-propylphenyl) with methyl triflate (MeOTf) leads to the formation of cationic diphosphane [((Cl)Im(Dipp))(Me)P-P(Cl)(Dipp)](+) (8+) in a stereoselective methylation. In contrast, reacting with the Lewis acid GaCl3 yields cationic diphosphene [((Cl)Im(Dipp))P=P(Dipp)](+) (7+), which is explained by a low P-Cl bond dissociation energy. The significantly polarized P=P double bond in 7+ allows for its utilization as an acceptor for nucleophiles - the reaction with Cl(-) regenerates diphosphanide and the reaction with PMe3 gives cation [((Cl)Im(Dipp))P-P(PMe3)(Dipp)] (9+). In depth DFT investigation provides detailed insights into the bonding situation of the reported compounds.
authors.affiliation: Chair of Inorganic Molecular Chemistry, University of Technology Dresden, 01062 Dresden, Germany. jan.weigand@tu-dresden.de.
authors.forename: Kai
authors.initials: K
authors.lastname: Schwedtmann
authors.affiliation: Chair of Inorganic Molecular Chemistry, University of Technology Dresden, 01062 Dresden, Germany. jan.weigand@tu-dresden.de.
authors.forename: Michael H
authors.initials: MH
authors.lastname: Holthausen
authors.affiliation: Chair of Inorganic Molecular Chemistry, University of Technology Dresden, 01062 Dresden, Germany. jan.weigand@tu-dresden.de.
authors.forename: Chris H
authors.initials: CH
authors.lastname: Sala
authors.affiliation: Chair of Inorganic Molecular Chemistry, University of Technology Dresden, 01062 Dresden, Germany. jan.weigand@tu-dresden.de.
authors.forename: Felix
authors.initials: F
authors.lastname: Hennersdorf
authors.affiliation: Institute of Organic Chemistry, Westfälische Wilhelms-Universität Münster, 48149 Münster, Germany.
authors.forename: Roland
authors.initials: R
authors.lastname: Fröhlich
authors.affiliation: Chair of Inorganic Molecular Chemistry, University of Technology Dresden, 01062 Dresden, Germany. jan.weigand@tu-dresden.de.
authors.forename: Jan J
authors.initials: JJ
authors.lastname: Weigand