title: Formation of cationic [RP5Cl](+)-cages via insertion of [RPCl](+)-cations into a P-P bond of the P4 tetrahedron.
abstract: Fluorobenzene solutions of RPCl(2) and a Lewis acid such as ECl(3) (E = Al, Ga) in a 1:1 ratio are used as reactive sources of chlorophosphenium cations [RPCl](+), which insert into P-P bonds of dissolved P(4). This general protocol represents a powerful strategy for the synthesis of new cationic chloro-substituted organophosphorus [RP(5)Cl](+)-cages as illustrated by the isolation of several monocations (21a-g(+)) in good to excellent yields. For singular reaction two possible reaction mechanisms are proposed on the basis of quantum chemical calculations. The intriguing NMR spectra and structures of the obtained cationic [RP(5)Cl](+)-cages are discussed. Furthermore, the reactions of dichlorophosphanes and the Lewis acid GaCl(3) in various stoichiometries are investigated to obtain a deeper understanding of the species involved in these reactions. The formation of intermediates such as RPCl(2)·GaCl(3) (14) adducts, dichlorophosphanylchlorophosphonium cations [RPCl(2)-RPCl](+) (16(+)) and [RPCl(2)-RPCl-GaCl(3)](+) (17(+)) in reaction mixtures of RPCl(2) and GaCl(3) in fluorobenzene strongly depends on the basicity of the dichlorophosphane RPCl(2) (R = tBu, Cy, iPr, Et, Me, Ph, C(6)F(5)) and the reaction stoichiometry.
authors.affiliation: Institut für Anorganische and Analytische Chemie, Westfaelische Wilhelms Universitaet Muenster, Corrensstrasse 30, 48149 Muenster, Germany.
authors.forename: Michael H
authors.initials: MH
authors.lastname: Holthausen
authors.forename: Kai-Oliver
authors.initials: KO
authors.lastname: Feldmann
authors.forename: Stephen
authors.initials: S
authors.lastname: Schulz
authors.forename: Alexander
authors.initials: A
authors.lastname: Hepp
authors.forename: Jan J
authors.initials: JJ
authors.lastname: Weigand