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Reaction of Me 3 SiNPCl 3  with AlCl 3  yields the donor-acceptor complex [Me 3 SiNPCl 3  · AlCl 3 ] (1). Thermal treatment of 1 and simultaneously removing the by-product Me 3 SiCl results in the formation of [Cl 2 AlNPCl 3 ] 2  (2). Crystallization of 2 from CH 2 Cl 2  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, R 1  = 0.0498). The molecule exhibits site symmetry C i  (point group approximately C 2h ) and shows as a characteristic feature a planar, almost square Al 2 N 2  four-membered ring with Al-N distances of 187.5(3) and 187.9(3) pm. The phosphorus atoms of the PCl 3 -groups attached to the nitrogen atoms are almost located in the same plane as defined by the Al 2 N 2 -ring. Both new compounds have been characterized by IR, NMR, and MS spectroscopy.

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Synthese, Kristallstruktur und Spektroskopische Charakterisierung des Phosphaniminato-Komplexes [Cl 2 AlNPCl 3 ] 2  und des Phosphanimin-Komplexes [Me 3 SiNPCl 3  · AlCl 3 ]/Synthesis, Crystal Structure, and Spectroscopic Characterization of the Phosphorane Iminato Complex [Cl 2 AlNPCl 3 ] 2 , and of the Phosphane Imine Complex [Me 3 SiNPCl 3  · AlCl 3 ]