HETEROBIMETALLIC (PD,PT,CU) COMPLEXES OF HEXAPYRAZOLYLCYCLOTRIPHOSPHAZENEVIASIMULTANEOUS GEMINAL (N2) AND NONGEMINAL (N3) COORDINATION MODES

Synthesis and spectroscopy of four heterobimetallic compounds containing the metal centres Cu(II)-Pd(II) and Cu(II)-Pt(II) with the multidentate nitrogen donor ligand hexakis (3,5-dimethyl-pyrazolyl)cyclotriphosphazene, (HPCTP) are reported. The complexes HPCTP·CuCl2·MX2 (M = Pd, X = Cl (3) or Br (4) and M = Pt, X = Cl (5) or Br (6)) were obtained by treating the metal-containing ligands HPCTP°CuX2 X = Cl(l) or Br(2)) with M(PhCN)2Cl2(M = Pd or Pt). The electronic absorption spectra and electron paramagnetic resonance data indicate the copper in these compounds has a distorted trigonal bipyramidal geometry. A single crystal X-ray determination of 4 is reported. The crystals of 4 are monoclinic with a = 10.570(2), b = 28.863(4), c = 16.009(1)A, β = 98.71(2)°, V = 4827(1)A3, Z = 4, D c = 1.65 g cm−3 and space group P21/c. The geometry about copper is trigonal bipyramidal with mean distances of Cu-N(pz) = 1.987(13), Cu-N(ctp) = 2.352(11) and Cu-Cl = 2.315(10)A while that of palladium is square plana...