1360002-55-6Relevant academic research and scientific papers
Formation of cationic [RP5Cl]+-cages via insertion of [RPCl]+-cations into a P-P bond of the P4 tetrahedron
Holthausen, Michael H.,Feldmann, Kai-Oliver,Schulz, Stephen,Hepp, Alexander,Weigand, Jan J.
, p. 3374 - 3387 (2012)
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 [RP 5Cl]+-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 RPCl 2?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.
