Oxidative Addition von N ‐Chlortriphenylphosphanimin an Phosphortrichlorid und Antimontrichlorid. Kristallstrukturen von (Cl 3 PNPPh 3 ) 2 [PCl 6 ][ClHCl],[SbCl 4 (HNPPh 3 ) 2 ][SbCl 6 ] und [Sb(NPPh 3 ) 4 ][SbCl 6 ]

Oxidative Addition of N ‐chlorotriphenylphosphoraneimine onto Phosphorus(III) Chloride and Antimony(III) Chloride. Crystal Structures of (Cl 3 PNPPh 3 ) 2 [PCl 6 ][ClHCl], [SbCl 4 (HNPPh 3 ) 2 ][SbCl 6 ], and [Sb(NPPh 3 ) 4 ][SbCl 6 ] Phosphorus(III) chloride reacts with N ‐chlorotriphenylphosphoraneimine, ClNPPh 3 , in CH 2 Cl 2 solution strongly exothermically via oxidative addition to give (Cl 3 PNPPh 3 ) 2 [PCl 6 ][ClHCl] ( 1 ). As a by‐product, Ph 3 PNP(O)Cl 2 can be obtained, which is formed from PCl 3 and ClNPPh 3 in the presence of POCl 3 . In contrast to these results, antimony(III) chloride reacts with ClNPPh 3 in CH 2 Cl 2 solution to give a mixture of the phosphoraneimine complex [SbCl 4 (HNPPh 3 ) 2 ][SbCl 6 ] ( 2 ) and the phosphoraneiminato complex [Sb(NPPh 3 ) 4 ][SbCl 6 ] ( 3 ). The complexes 1 ‐ 3 were characterized by IR spectroscopy and by single crystal X‐ray determinations. 1 : Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 3282.0(2), b = 798.7(1), c = 1926.1(2) pm, β = 107.96(1)°, R 1 = 0.0302. 1 contains [Cl 3 PNPPh 3 ] + cations with PN bond lengths of 152.5(2) and 160.9(2) pm, and a PNP bond angle of 140.5(1)°. 2 ·CH 2 Cl 2 : Space group ${\rm P}{\bar 1}$ , Z = 2, lattice dimensions at 193 K: a = 1031.2(1), b = 1448.3(2), c = 1811,4(2) pm, α = 70.96(1)°, β = 87.67(1)°, γ = 75.37(1)°, R 1 = 0.0713. 2 ·CH 2 Cl 2 contains cations [SbCl 4 (HNPPh 3 ) 2 ] + with octahedrally coordinated Sb atom and the HNPPh 3 ligand molecules being in trans ‐position. Sb–N bond lengths are 207.6(6) and 209.3(6) pm, PN bond lengths 162.3(7) and 160.8(7), which approximately corresponds with double bonds. 3 ·0.5CH 2 Cl 2 : Space group P4/n, Z = 2, lattice dimensions at 193 K: a = b = 1678.8(1), c = 1244.3(1) pm, R 1 = 0.0618. 3 ·0.5CH 2 Cl 2 contains [Sb(NPPh 3 ) 4 ] + cations with tetrahedrally coordinated Sb atom and short Sb–N bond lengths of 193.7(6) pm. The PN distances of the phosphoraneiminato ligands, (NPPh 3 ) − with 156.5(6) pm, correspond with double bonds, the SbNP bond angles are 130.6(3)°.