Synthesis and Catalytic Application of Dinuclear Nickel and Copper Complexes
Date Issued
2011
Date
2011
Author(s)
Cheng, Ting-Peng
Abstract
Abstact
We have successfully prepared and characterized dinuclear nickel and copper complexes containing 2,7-di(R2-pyrazolyl)-1,8-naphthyridine (La R = H, Lb R = Me,
Lc = Ph) and have studied the application in this thesis.
Reaction of La ~Lc with NiCl2 provided the dinickel complex
[(Lx)Ni2Cl4(CH3OH)2] (X = a~b) (5a~5b). X-ray crystal determinations show that this series of nickel complexes are six coordinate. Treatment of sodium trifluoroacetate with 5a resulted in the formation of trifluoroacetate substituted species, which was characterized by UV, IR and mass spectroscopy. Treatment of La and Lb with [Cu(CH3CN)4PF6] yielded the dinuclear copper complexes
[(Lx)Cu2(CH3CN)4]．2PF6 (x = a, b) (7a~7b), which were heating in the co-solvents (acetone/chloroform) in the presence of chloride resulted in the formation of [(Lx)Cu2Cl2] (x = a~c) (8a~c). For the synthesis of iridium complex via the treatment of La with IrCl3．3H2O yielded [[(La)Ir(H2O)Cl3], a mono-nuclear species. X-ray structural characterization showed that mononuclear iridium complex is the six coordinate structural.In the catalytic application, dinuclear nickel complexes do show the activity on the oxidative homo-coupling of the terminal alkynes. Complex 5a and 5c afforded the corresponding 1,3-diyne product with good yields with dioxygen as the oxidant under mild conditions (35oC).
Subjects
Dinuclear Nickel
Copper
Type
thesis
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