Die Kristallstrukturen der Phosphanimin‐Komplexe [NaI(HNPPh3)3] und [SrI2(HNPPh3)2(THF)2] sowie des Natrium‐triphenylphosphaniminats [NaNPPh3]6

Crystal Structures of the Phosphaneimine Complexes NaI(HNPPh₃)₃] and SrI₂(HNPPh₃)₂(THF)₂], as well as of Sodium Triphenylphosphoraneiminate NaNPPh₃]₆ NaI(HNPPh₃)₃] ( 1 ) has been obtained as yellow, moisture sensitive crystals as an intermediate product of the synthesis of sodium triphenylphosphoraneiminate, NaNPPh₃]₆ ( 2 ) from Ph₃PI₂ and sodium amide in liquid ammonia. Correspondingly, colourless crystals of SrI₂(HNPPh₃)₂(THF)₂] ( 3 ) are formed from strontium amide and Ph₃PI₂ in liquid ammonia and subsequent recrystallisation of the primary product SrI₂(HNPPh₃)₄] from thf solution. The complexes 1 – 3 are mainly characterized by crystal structure determinations. 1 · 0,5 thf: space group P3c1, Z = 4, lattice dimensions at 193 K: a = b = 1533.2(1); c = 2545.6(1) pm, R = 0.0417. 1 has a molecular structure in which the sodium atom is tetrahedrally coordinated by the iodine atom with a distance of 315.9 pm and by the nitrogen atoms of the three HNPPh₃ molecules with a distance of 238.9 pm. 2 · C₇H₈: space group P1, Z = 1, lattice dimensions at 213 K: a = 1457.1(1), b = 1484.9(1), c = 1502.7(1) pm; α = 116.32(1)°, β = 115.358(10)°, γ = 93.585(14)°; R = 0.0520. 2 has a molecular structure in which the six sodium atoms and the six nitrogen atoms of the (NPPh₃^–) groups form a hexagonal prism with approximate D_3d symmetry. 3 · 2 thf: space group P1, Z = 2, lattice dimensions at 193 K: a = 1042.9(1), b = 1337.4(1), c = 2095.1(1) pm; α = 90.130(8)°, β = 96.310(8)°, γ = 111.985(8)°; R = 0.0310. 3 has a molecular structure in which the strontium atom is octahedrally coordinated by the iodine atoms, by the nitrogen atoms of the HNPPh₃ molecules and by the oxygen atoms of the thf molecules, all ligands being in trans‐position to one another.