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]

摘要

Phosphorus(III) chloride reacts with N-chlorotriphenyl-phosphoraneimine, ClNPPh3, in CH2Cl2 solution strongly exothermically via oxidative addition to give (Cl3PNPPh3)(2)[PCl6][ClHCl] (1). As a by-product, Ph3PNP(O)Cl-2 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, beta = 107.96(1)degrees, R-1 = 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)degrees. 2(.)CH(2)Cl(2): Space group P1, Z = 2, lattice dimensions at 193 K: a = 1031.2(1), b = 1448.3(2), c = 1811,4(2) pm, alpha = 70.96(1)degrees, beta = 87.67(1)degrees, gamma = 75.37(1)degrees, R-1 = 0.0713. 2(.)CH(2)Cl(2) 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(.)0.5CH(2)Cl(2): Space group P4, 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(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)degrees.