| Abstrakt: |
The reaction of hexakis2-pyridyloxycyclotriphosphazene L and hexakis4-methyl-2-pyridyloxycyclotriphosphazene MeL with copperii chloride afford the complexes CuLCl2, CuCl22MeL, CuLClPF6and CuMeLClPF6. The single-crystal X-ray structure of CuLCl2 shows the copper ion to be in a square based pyramidal distorted trigonal bipyramidal SBPDTBP environment τ 0.47 with L acting as a κ3Ndonor, coordinating viathe nitrogen atoms from two non-geminal pyridyloxy pendant arms, a nitrogen atom in the phosphazene ring and two chloride ions. In the dimetallic complex, CuCl22MeL, the geometry about both symmetry related copperii centres is also SBPDTBP τ 0.57 with a ‘N3Cl2’ donor set. In the monocation of CuLClPF6, L acts as a κ5Ndonor, bonding to the copperii centre through the nitrogen atoms of four pyridyloxy pendant arms, a phosphazene ring nitrogen atom and a chloride ion to give an elongated rhombic octahedral coordination sphere. The phosphazene ring atoms remain virtually coplanar in all three structures as a consequence of the phenoxy-hinge, which links the pyridine pendant donors to the cyclotriphosphazene platform, allowing the formation of six-membered chelate rings. The spectroscopic mass spectral, EPR and electronic and magnetic properties of the complexes are discussed. The EPR and variable temperature magnetic susceptibility results for the dicopper complex, CuCl22MeL, point to a very weak electronic interaction between the metal atoms. |
