| The chemistry of molybdenum sulfur complexes have received much attention not only because of their diverse structural chemistry but also due to their potential applications in industrial catalytic systems and optoelectronic materials.Treatment of[Et4N]2[Mo S4]with S8 gave a mixture of[Et4N]2[Mo S?S4?2]with the terminal Mo=S bond and[Et4N]2[Mo O?S4?2]with the terminal Mo=O bond.Interaction of[Et4N]2[Mo S?S4?2]with equal equivalent a series of dithiolate ligands such as 1,2-benzenedithiol?H2bdt?,3,6-dichloro-2-benzenedithiol?H2bdt Cl2?,toluene-3,4-dithiol?H2tdt?,dimethyl acetylene dicarboxylate?DMAC?,1,2-dicyano-ethyldithiol?H2tmid?,bis?trifluoromethyl?-1,2-dithiol?H2tfd?,1,3-dithian-2-one-4,5-dithiol?H2dmid?afforded fourteen mono-and bi-nuclear molybdenum-sulfur complexes,of which single-crystals of three complexes were obtained and their molecular structures were established by X-ray crystallography,such as[Et4N]2[Mo O?S4??bdt Cl2?]?7?,[Et4N]2[Mo O?bdt Cl2?]2??-S?2?8?and[Et4N]2[Mo O-?bdt?]2??-S?2?9?.All complexes were well characterized by FT-IR and 1H NMR along with their macroanalyses.To explore formation of macro-ring based upon the typical{Mo2??-S?2O2}2+unit,Cs2[Mo10O10??-S?10??-OH?10?H2O?5]?C8H6O6?2·15H2O?15?formed from self-assembly in the presences of Cs Cl and 2,5-dihydroxylterephthalic acid.The present molecular structure of Mo10-ring was established by X-ray crystallography and it was also characterized by spectroscopy and electrochemistry.To understand the relationship between structure and catalytic property,the electrochemical properties for electron-catalytic activity of this Mo10-ring cluster were investigated in detail,which is expected to design a family of transition metal sulfur clusters with the terminal molybdenum-sulfur double bonds and the bridged molybdenum-sulfur single bonds. |
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