Synthesis and Catalytic Application of Dimetal Complex with Pyrazolylnaphthyridine Ligand
Date Issued
2013
Date
2013
Author(s)
Tsai, Chia-Min
Abstract
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.
Subjects
雙銅錯合物
Type
thesis
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