| Abstract: | Oxidative Addition of N‐chlorotriphenylphosphoraneimine onto Phosphorus(III) Chloride and Antimony(III) Chloride. Crystal Structures of (Cl3PNPPh3)2[PCl6][ClHCl], [SbCl4(HNPPh3)2][SbCl6], and [Sb(NPPh3)4][SbCl6] Phosphorus(III) chloride reacts with N‐chlorotriphenylphosphoraneimine, ClNPPh3, in CH2Cl2 solution strongly exothermically via oxidative addition to give (Cl3PNPPh3)2[PCl6][ClHCl] ( 1 ). As a by‐product, Ph3PNP(O)Cl2 can be obtained, which is formed from PCl3 and ClNPPh3 in the presence of POCl3. In contrast to these results, antimony(III) chloride reacts with ClNPPh3 in CH2Cl2 solution to give a mixture of the phosphoraneimine complex [SbCl4(HNPPh3)2][SbCl6] ( 2 ) and the phosphoraneiminato complex [Sb(NPPh3)4][SbCl6] ( 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)°, R1 = 0.0302. 1 contains [Cl3PNPPh3]+ cations with PN bond lengths of 152.5(2) and 160.9(2) pm, and a PNP bond angle of 140.5(1)°. 2 ·CH2Cl2: Space group , 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)°, R1 = 0.0713. 2 ·CH2Cl2 contains cations [SbCl4(HNPPh3)2]+ with octahedrally coordinated Sb atom and the HNPPh3 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 ·0.5CH2Cl2: Space group P4/n, Z = 2, lattice dimensions at 193 K: a = b = 1678.8(1), c = 1244.3(1) pm, R1 = 0.0618. 3 ·0.5CH2Cl2 contains [Sb(NPPh3)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, (NPPh3)? with 156.5(6) pm, correspond with double bonds, the SbNP bond angles are 130.6(3)°. |
