A PH-functionalized dicationic bis(imidazolio)diphosphine

Abstract

Reaction of the iodide salt of a secondary imidazolio-iodophosphine [(L)PHI]I (L⁺ = 1,3-diarylimidazolium-yl) with an imidazolio-phosphide (L)PH in the presence of GaI₃ afforded the isolable salt of a dicationic, bis(imidazolio)-substituted dihydro-diphosphine [(L)₂P₂H₂][GaI₄]₂. Non-preparative formation of the cationic diphosphines was also observed upon spontaneous "dehalo-coupling" of [(L)PHI]⁺, or in reactions of [(L)PHI]I and (L)PH in the absence of GaI₃. Further reaction of [(L)₂P₂H₂]²⁺ with (L)PH produced an iodide salt of a known (bis)imidazolio-diphosphide monocation [(L)₂P₂H]⁺. The identity of cationic diphosphines and diphosphides was established by single-crystal X-ray diffraction studies. NMR spectroscopy revealed that dications [(L)₂P₂H₂]²⁺ exist as a mixture of meso- and rac-diastereomers in solution. Computational studies confirmed the stereochemical assignment of the isomers observed, and gave insight into the bonding situation of the diphosphine dications.