Syntheses And Crystal Structures Of Cu/Ag Compounds With N-/P-Containing Ligands

In the past decades, particular attention has been devoted to the complexes of copper and silver atoms with N- or P-containing ligands because of their potential aplications in biochemical systems, industrial catalysts, magnetical and photoelectronic materials.In this thesis, reactions of silver, copper or mercury salts with dmpzm (dmpzm = Bis(3,5-dimethylpyrazol-1-yl)methane) and dppm (Ph2PCH2PPh2) or dppe (Ph2PCH2 CH2PPh2),resulted in the formation of five complexes [Cu3(dmpzm)4(μ-1, 3-dca)2(dca)4]·2H2O (1) (dca = dicyanamide), [Cu2(dmpzm)2(μ-dppe) (MeCN)2] (ClO4)2·(MeCN)2 (2), [Cu2(μ-η1:η1-dppm)2(μ-MeCN)(MeCN)2] (ClO4)2·Me CN (3), [Ag(dmpzm)(CN)]2 (4), and [(dmpzm)HgI2] (5), respectively. Complexes 1, 2, 4, 5 were characterized by elemental analysis, IR and thermogravimetric analysis. The crystal structures of compounds 1～5 were determined by X-ray crystallography.Compound 1 can be viewed as a "see-saw" shaped structure in which the central [Cu(dmpzm)2]2+ fragment and two side [Cu(dmpzm)(dca)2] units are linked by a pair ofμ-1,3-dca bridges. Complex 2 consists of two [Cu(dmpzm)(MeCN)] fragments interconnected by a dppe ligand, forming a dimeric structure. In the structure of 3, the two Cu atoms are bridged by two dppm ligands and one acetonitrile molecule. Each Cu atom is coordinated by two N atoms of two different MeCN molecules and two P atoms of different dppm ligands forming distorted tetrahedral coordination geometry. Compound 4 has dinuclear silver dimeric structre in which the Ag atom adopts distorted tetrahedral geometry. In 5, each Hg atom is coordinated by two I atoms and two N atoms of the dmpzm group, forming distorted tetrahedral coordination geometry. The thermogravimetric properties of 1, 2 and 4 were studied.