Phosphaniminato-Cluster des Kupfers. Synthese und Kristallstrukturen von [Cu6Cl6(NPMe3)4]Cl[Me3SiNPMe3] · CH2Cl2 und [Cu6Cl6(NPMe3)4][Cu(Me3SiNPMe3)2]Cl2 / Phosphoraneim inato Clusters of Copper. Syntheses and Crystal Structures of [Cu6Cl6(NPMe3)4]Cl[Me3SiNPMe3] · CH2Cl2 and [Cu6Cl6(NPMe3)4][Cu(Me3SiNPMe3)2]Cl2

Abstract

Abstract The title compounds have been prepared as black-blue crystals with metallic lustre by the reaction of CuCl2 and CuCl, respectively, with Me3SiNPMe3 in CH2Cl2 suspensions. The complexes have been characterized by cyclic voltammetry and by crystal structure determinations. [Cu6Cl6(NPMe3)4]Cl[Me3SiNPMe3] · CH2Cl2: Space group P212121, Z = 4, structure solution with 4407 unique observed reflections, R = 0.057. Lattice dimensions at -70 °C: a -1159.3(8), b = 2027.1(14), c = 2063.3(12) pm. The compound consists of cluster ions [Cu6Cl6(NPMe3)4]+, in which the copper atoms form a regular octahedron. Four planes of the octahedra are capped by μ3-nitrogen atoms of the (NPMe3)- groups. Each of the Cu atoms is connected with a terminal chlorine atom . Another chloride ion serves for charge compensation; this ion occupies another Cu3 plane of the octahedron. Without bonding interaction one Me3SiNPMe3 molecule and one CH2Cl2 molecule are included in the lattice. [Cu6Cl6(NPMe3)4][Cu(Me3SiNPMe3)2]Cl2: Space group Pna21, Z = 4, structure solution with 5676 unique observed reflections, R = 0.071. Lattice dimensions at -70 °C: a = 3117.2(21), b = 1927.4(11), c = 1002.7(8) pm. The compound consists of cluster ions [Cu6Cl6(NPMe3)4]+, the complex ion [Cu(Me3SiNPMe3)2]+, and chloride ions. In the cation [Cu(Me3SiNPMe3)2]+ the copper atom is linearly coordinated by the nitrogen atoms of the phosphaneimine molecules.