Conformationally rigid chelate rings in metal complexes of pyridyloxy-substituted 2,2'-dioxybiphenyl-cyclotetra- and cyclotriphosphazene platforms

Divalent metal halides react with pyridyloxy-substituted 2,2'-dioxybiphenyl-cyclotri- and cyclotetraphosphazene ligands to form the complexes, MLX2] M=Co or Cu; L=(2,2'-dioxybiphenyl)tetrakis(2-pyridyloxy)cyclotriphosphazene (L1) or (2,2'-dioxybiphenyl)tetrakis(4-methyl-2-pyridyloxy)cyclotriphosphazene (L2); X=Cl or Br], ZnLCl2] L=bis(2,2'-dioxybiphenyl)bis(2-pyridyloxy)cyclotriphosphazene (L3) or bis(2,2'-dioxybiphenyl)bis(4-methyl-2-pyridyloxy)cyclotriphosphazene (L4)], MLCl2] M=Cu or Hg; L=tris(2,2'-dioxybiphenyl)bis(2-pyridyloxy)cyclotetraphosphazene (L5)] and Cu2LCl4] (L=trans-bis(2,2'-dioxybiphenyl)tetrakis(2-pyridyloxy)cyclotetraphosphazene (L6)]. Single-crystal X-ray structures show the L2 ligand complexes to have a N3Cl2 five-coordinate, trigonal-bipyramidal donor set with the phosphazene ring and pendant pyridyloxy nitrogens binding to the metal ions. The coordinated L2 ligand in the complex, CoL2Cl2], slowly hydrolyses in acetonitrile with the loss of a pyridine pendant arm to form a dimetallic species, which has been characterized by crystallography as {CoL2aCl}]2.4MeCN (L2a=N3P3(biph)(OPy)3(O)]-, biph=2,2'-dioxybiphenyl, OPy=2-oxopyridine). The ligands, L3, L4, L5, and L6, bind to the metal halides via gem-substituted pyridyloxy nitrogens only. The resulting rigid eight-membered chelate rings all have distorted boat conformations, which force distorted-tetrahedral N2Cl2 coordination environments onto the metal ions. The spectroscopic (ESR and electronic) and magnetic properties of the complexes are reported.