| Summary: | 碩士 === 國立臺灣大學 === 化學研究所 === 102 === This work involves the coordination study of multidentate dinucleating ligand 2,7-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,8-naphthyridine (4) with copper and ruthenium precursor and catalytic activity of the resulting dicopper complex.
Reaction of 4 with [Cu(CH3CN)4]PF6 provided the dicopper complex [(4)Cu2(CH3CN)4].2PF6 (5).In addition, oxidation of 5 in acetic acid produced Cu(II) complex [(4)Cu2(CH3COO)3(OH)] (11). Coordination of 4 with CuBr and CuI resulted in the formation of dinuclear copper complexes [(4)Cu2Br2] (6) and [(4)Cu2I2] (7), respectively. Both 6 and 7 contain halides as bridging_ligands. Treatment of 4 with [Ru(benzene)Cl2]2 afforded the mononuclear ruthenium complex [(4)Ru(benzene)Cl2] (8). All complexes were characterized by spectroscopic methods. Structure of ruthenium complex 8 was further confirmed by X-ray crystallography.
In the catalytic application, dinuclear copper complexes were active for the oxidative homocoupling of the terminal alkynes under basic conditions. In the presence of base and complex 5, terminal alkynes underwent homocoupling to afford the corresponding symmetrical 1,3-diynes in moderate to good yields with dioxygen as the oxidant under mild condition. Comparison of activities of metal complexes including Cu(II) were investigated.
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