Synthesis, Structure And Properties Of Copper Halide Coordination Polymers And Rare Earth Phosphonate Complexes

The copper(I) halide complexes show colorful structural chemistries because of the diversity of coordination geometry of univalence copper ion and the potential capability of halide ions as bridging ligand. In the presence of aromatic amine, organophosphine or organoarsine, it is prone to form neutral complexes, whose general formula is (CuX)mLn, [(CuX)mB]n or [(CuXL)mB]n (B is polydentate bridging ligand, and L is monodentate or polydentate chelating ligand). In the complex, if there is only monodentate or polydentate chelating ligand, copper halides themselves tend to form isolated clusters or oligomers with many structure types; If there is polydentate bridging ligand, the isolated clusters or oligomers can be linked by it and high-dimention polymers can be obtained.Since trivalence rare earth ions are Lewis hard acid and are very oxophilic, they are expected to interact strongly with highly polarized oxygen-bearing functional groups to form a number of complexes and polymers with special structures, which can be used as catalysts and extractants. The ligands involving phosphoryl (P=O) group are favorable to coordinate to lanthanide ions and actinide ions, and have been applied in the solvent extract and separation process. The syntheses, structures and catalysis properties of rare earth complexes and polymers with diphosphonate have been extensively attracted.1 The copper(I) complex, [Cu2Cl2(PPh3)2(2-Amp)]∞, has been synthesized by the reaction of copper(I) halide with 2-aminopyrimidine as bridging ligand and triphenylphosphine as monodentate ligand in methylene dichloride. It has been structurally characterized by X-ray diffraction. The crystal structure of the compound is built of one-dimensional chains, which are formed by two crystallographically independent [Cu2Cl2(PPh3)2(2-Amp)] dimer units bridged by each two N atoms from the pyrimidine rings of 2-aminopyrimidine.2 A number of solid rare earth complexes with the compounds involving phosphoryl (P=O) group as the first ligand and the compounds involving nitrogen atom as auxiliary ligand have been synthesized. The compounds involving phosphoryl (P=O) group are tetraisopropylmethylenediphosphonate ((iPrO)2P(O)CH2P(O)(OiPr)2), triphenylphosphine (Ph3PO) and bis(diphenylphosphino)methane (Ph2P(O)CH2P(O)Ph2). The auxiliary ligands are phenanthroline(phen), 2-aminopyrimidine(2-Amp), 2-mercaptobenzothiazole(2-mbt), 2,2'-bipyridine(2,2'-bpy), imidazole(im), benzimidazole (benzim), pyrazine(pyz), quinoline(quin) and 4,4'-bipyridine(4,4'-bpy), etc. Eight diphosphonate complexes with phenanthroline are selected to be characterized by element analysis, TG-DTA analysis, infrared spectra, 1H NMR, 31P NMR and luminescence spectra.3 Chiral tetraalkylmethylenediphosphonate, (R*O)2(O)PCH2P(O)(OR*)2 (R*=C10H19), has been synthesized by the reaction of methylenebis(phosphonic dichloride), CH2(POCl2)2, and chiral alcohol, R*OH (R*=C10H19), and has been characterized by element analysis, infrared spectra, 1H NMR, 31P NMR and CD spectra. In addition, three new chiral rare earth complexes with the chiral ligand have been prepared and characterized by infrared spectra...