Formation of Cationic [RP5Cl]+-Cages via Insertion of [RPCl]+-Cations into a P–P Bond of the P4 Tetrahedron

Fluorobenzene solutions of RPCl2 and a Lewis acid such as ECl3 (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 P4. This general protocol represents a powerful strategy for the synthesis of new cationic chloro-substituted organophosphorus [RP5Cl]+-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 [RP5Cl]+-cages are discussed. Furthermore, the reactions of dichlorophosphanes and the Lewis acid GaCl3 in various stoichiometries are investigated to obtain a deeper understanding of the species involved in these reactions. The formation of intermediates such as RPCl2·GaCl3 (14) adducts, dichlorophosphanylchlorophosphonium cations [RPCl2–RPCl]+ (16+) and [RPCl2–RPCl–GaCl3]+ (17+) in reaction mixtures of RPCl2 and GaCl3 in fluorobenzene strongly depends on the basicity of the dichlorophosphane RPCl2 (R = tBu, Cy, iPr, Et, Me, Ph, C6F5) and the reaction stoichiometry.