Syntheses And Structural Characterizations Of Series Copper(?) And Silver(?) Cluster Complexes With Bidentate Phosphine Ligands

Syntheses and structral characterization of series copper(?) and silver(?) complexes with bidentate phosphine ligands was reported in this thesis. The bidentate bis(diphenylphosphino)alkane ligands Ph2P(CH2)x PPh2(x=1-3) were selected to react with copper(?) and silver(?) halides under the circumstance of different reactants ratio and solvents, which leading to eight different structural complexes. Treatment of AgBr with bis(diphenylphosphino)methane(dppm) which the ligand to metal ratio 3:4 or bis(diphenylphosphino)ethane(dppe) in the presence of [Et4N]Br in THF/MeCN gave a trinuclear cationic trigonal-bipyramid complex [Ag3(m3-Br)2(m-dppm)3][AgBr2](1) with a linear [AgBr2]- anion; while treatment of AgC l with dppm in THF/MeCN or in CH2Cl2 in the presence of KPF6 afforded a trinuclear cationic trigonal-bipyramid complex [Ag3(m3-Cl)2(m-dppm)3][PF6]×2THF(2) with two tetrahydrofuran solvent molecules or [Ag3(m3-Cl)2(m-dppm)3][PF6](3), respectively. The reaction of C uC l with dppm in THF/MeCN or in CH2Cl2 in the presence of KPF6 led to [Cu3(m3-Cl)2(m-dppm)3][PF6](4) and [C u3(m3-Cl)2(m-dppm)3]C l×THF(5) in which their anions were different; Treatment of AgBr with bis(diphenylphosphino)ethane(dppe) in the presence of [Et4N]Br in THF/MeCN gave a dinuclear anionic polymeric complex {[Et4N][Ag2(m-Br)3(m-dppe)]}n(6) with a [Ag2(m-Br)3] core, respectively; Reaction of AgC l with bis(diphenylphosphino)ethane(dppe) or bis(diphenylphosphino)propane(dppp) in which the metal to ligand ratio was 1:1 in MeCN or MeCN/NH2(CH2)2NH2 in the presence of [Et4N]C l to provide organic cations resulted in isolation of a dinuclear anionic complex [Et4N]2[(AgC l2)2(m-dppe)](7) with one m-dppe bridge or a dinuclear neutral complex [(AgC l)2(m-dppp)2](8) with two m-dppp bridges and a 12- membered ring, respectively;. The eight complexes were characterized by ?R, 1H NMR, MS and Elemetal Analysis, and their structures were established by single crystal X-ray diffraction. 1, 2, 3, 4 and 5 were trinuclear metal cluster complexes with a [M3(m-X)2] core in which each halogen bridged three metal atoms with almost a trigonal-bipyramid unit. The distance between Ag···Ag was 3.373(1) ? in complexes 1 similar to complexes 2 and 3, and the average length of six Ag–Br bonds(1) was 2.829(1) ?, which was obviously longer than Ag–C l bond lengh of complexes 2 and 3(2.704(1) ?); While in complexes 4 and 5, the average distance between C u···Cu was 3.125(1) ?, which was approximately 0.25 ? shorter than the distance between Ag···Ag. A dinuclear anionic polymeric complex 6 with a [Ag2(m-Br)3] core had one–dimentional catenulate structure, while 7 and 8 were binuclear metal complexes in which the silver atom was chelated with three other atoms.