PHOSPHORANEIMINATO CLUSTERS OF COPPER - S YNTHESES AND CRYSTAL-STRUCTURES OF L6(NPME(3))(4)]CL[ME(3)SINPME(3)]CENTER-DOT-CH2CL2 AND [CU6CL6(NPME(3))(4)][CU(ME(3)SINPME(3))(2)]CL(2)

The title compounds have been prepared as black-blue crystals with met allic lustre by the reaction of CuCl2 and CuCl2 respectively, with Me( 3)SiNPMe(3) in CH2Cl2 suspensions. The complexes have been characteriz ed by cyclic voltammetry and by crystal structure determinations. [Cu6 Cl6(NPMe(3))(4)]Cl[Me(3)SiNPMe(3)].CH2Cl(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 degrees C: a = 1159.3(8), b = 2027.1 (14), c = 2063.3(12) pm. The compound consists of cluster ions [Cu6Cl6 (NPMe(3))(4)](+), in which the copper atoms form a regular octahedron. Four planes of the octahedra are capped by mu(3)-nitrogen atoms of th e (NPMe(3))(-) groups. Each of the Cu atoms is connected with a termin al chlorine atom. Another chloride ion serves for charge compensation; this ion occupies another Cu-3 plane of the octahedron. Without bondi ng interaction one Me(3)SiNPMe(3) molecule and one CH2Cl2 molecule are included in the lattice. [Cu6Cl6(NPMe(3))(4)][Cu(Me(3)SiNPMe(3))(2)]C l-2: Space group Pna2(1), Z = 4, structure solution with 5676 unique o bserved reflections, R = 0.071. Lattice dimensions at -70 degrees C: a = 3117.2(21), b = 1927.4(11), c = 1002.7(8) pm. The compound consists of cluster ions [Cu6Cl6(NPMe(3))(4)](+), the complex ion [Cu(Me(3)SiN PMe(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.