Iminophosphoranyl Dichlorophosphines R 3 PNPCl 2

The iminophosphoranyl dichlorophosphines Ph 3 PNPCl 2 ( 2a ), p Tol 3 PNPCl 2 ( 2b ), and Cy 3 PNPCl 2 ( 2c ) were synthesized by reaction of trimethylsilyliminophosphoranes R 3 PNSiMe 3 ( R = Ph, p Tol, Cy) with an equimolar amount of PCl 3 . The compounds 2b and 2c were isolated in pure form for the first time and characterized by 31 P, 1 H and 13 C NMR spectroscopy. The molecular structures of the iminophosphoranyl dichlorophosphines 2a – c were determined by single‐crystal X‐ray diffraction. In all cases the P–Cl bonds are elongated due to the influence of the strong electron donating iminophosphoranyl group. Compounds 2a – c are the first iminophosphoranyl dichlorophosphines, which could be characterized by X‐ray diffraction studies.