Synthese, Kristallstruktur und Spektroskopische Charakterisierung des Phosphaniminato-Komplexes [Cl2AlNPCl3]2 und des Phosphanimin-Komplexes [Me3SiNPCl3 · AlCl3]/Synthesis, Crystal Structure, and Spectroscopic Characterization of the Phosphorane Iminato Complex [Cl2AlNPCl3]2, and of the Phosphane Imine Complex [Me3SiNPCl3 · AlCl3]

Abstract

Reaction of Me3SiNPCl3 with AlCl3 yields the donor-acceptor complex [Me3SiNPCl3 · AlCl3] (1). Thermal treatment of 1 and simultaneously removing the by-product Me3SiCl results in the formation of [Cl2AlNPCl3]2 (2). Crystallization of 2 from CH2Cl2 yields colorless crystals which have been characterized by single crystal X-ray diffraction analysis (P1̄, a = 719.1(2), b = 843.5(2), c = 857.4(2) pm, α = 64.23(1), β = 76.62(1), γ = 68.21(1)°, Z = 1, R1 = 0.0498). The molecule exhibits site symmetry Ci (point group approximately C2h) and shows as a characteristic feature a planar, almost square Al2N2 four-membered ring with Al-N distances of 187.5(3) and 187.9(3) pm. The phosphorus atoms of the PCl3-groups attached to the nitrogen atoms are almost located in the same plane as defined by the Al2N2-ring. Both new compounds have been characterized by IR, NMR, and MS spectroscopy.