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 CuCl 2 and CuCl, respectively, with Me 3 SiNPMe 3 in CH 2 Cl 2 suspensions. The complexes have been characterized by cyclic voltammetry and by crystal structure determinations. [Cu 6 Cl 6 (NPMe 3 ) 4 ]Cl[Me 3 SiNPMe 3 ] · CH 2 Cl 2 : Space group P2 1 2 1 2 1 , 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 [Cu 6 Cl 6 (NPMe 3 ) 4 ] + , in which the copper atoms form a regular octahedron. Four planes of the octahedra are capped by μ 3 -nitrogen atoms of the (NPMe 3 ) - groups. Each of the Cu atoms is connected with a terminal chlorine atom . Another chloride ion serves for charge compensation; this ion occupies another Cu 3 plane of the octahedron. Without bonding interaction one Me 3 SiNPMe 3 molecule and one CH 2 Cl 2 molecule are included in the lattice. [Cu 6 Cl 6 (NPMe 3 ) 4 ][Cu(Me 3 SiNPMe 3 ) 2 ]Cl 2 : Space group Pna2 1 , 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 [Cu 6 Cl 6 (NPMe 3 ) 4 ] + , the complex ion [Cu(Me 3 SiNPMe 3 ) 2 ] + , and chloride ions. In the cation [Cu(Me 3 SiNPMe 3 ) 2 ] + the copper atom is linearly coordinated by the nitrogen atoms of the phosphaneimine molecules.