| Abstract: | The structure of the copper(II) chloride-triphenylphosphine-N-(2-pyrimidyl)imine complex in crystal and solution was investigated by x-ray analysis and EPR. It was found that despite the difference in the structures of the dissolved and crystalline complexes, the exocyclic nitrogen atom is contained in the coordination sphere of the metal together with the nitrogen atom of the heterocycle in both cases due to the electronic effect of the phosphorus atom. In the crystal, the copper atom is coordinated with two chlorine atoms and two molecules of the ligand, and the distance from the copper cation to the nitrogen atoms of the pyrimidine rings is significantly less than the distance to the nitrogen atoms of the phosphinimine groups (2.0 and 2.8 Å, respectively). The coordination polyhedron formed as a result is a strongly distorted axially asymmetric octahedron. In dissolution, the chlorine anions are substituted by molecules of the solvent, the complex acquires axial symmetry, and four nitrogen atoms from two ligands form a planar square with a copper(II) cation in the center.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 118–125, January, 1992. |
