| Summary: | 碩士 === 中原大學 === 化學研究所 === 89 ===
Abstract
A series novel MI (M = Cu, Ag) complexes of 1-(diethoxyphosphinyl) -1-cyanoethlene-2,2-dithiolates (cpdt) have been prepared and characterised by X-Ray diffraction methods, NMR spectroscopy ( 31P{1H}, 1H ), FAB mass spectrometry, IR spectroscopy, elemental analysis and melting point.
Two AgI-S and four CuI-S polynucler clusters containing bridging dppm and cpdt ligands were isolated from the reaction of M2(µ-dppm)2(CH3CN)2(PF6)2 and K2S2CC(CN)P(O)(OEt)2 in CH2Cl2 [M = Ag, Cu] , whereas the 1,1-dithiolates in Ag5(µ-dppm)4[S2CC(CN) P(O)(OEt)2]2 (PF6), 2 and Cu5(µ-dppm)4[S2CC(CN)P(O)(OEt)2]2(PF6), 5 exhibit a rare tetrametallic hexaconnective coordination pattern □3(µ2-S-µ3-S’-O), but in Cu9(µ-dppm)4[S2CC(CN)P(O)(OEt)2]4(PF6), 6. Exhibit an unprecedented pentametallic hexaconnective coordination mode □4(µ2-S-µ2-S’-O-N). In addition, tetranuclear clusters of the type, M4(µ-dppm)4[S2CC(CN)P(O)(OEt)2]2 (M = Ag, 1; Cu, 3), where the cpdt dislays an unusual tetradentate ligand bridging mode, were also characterized. Interestingly, the cluster Cu4(µ-dppm)3(dppmO)[S2CC(CN) P(O)(OEt)2]2 , 4, consists of dangling dppm with the phosphine oxide at the end.
Polynuclear d10 metal complexes always have luminescent properties, and we present the UV-Vis、excitation and emission spectra of complexes 1 ~ 6.
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