- 學位論文
雙鎳與雙銅金屬錯合物的合成及其催化應用
Synthesis and Catalytic Application of Dinuclear Nickel and Copper Complexes
摘要
摘要 本篇論文的主要內容合成具有2,7-di(R2-pyrazolyl)-1,8-naphthyridine (La R=H,Lb R=Me, Lc R=Ph)多牙氮配位基的鎳和銅雙金屬錯合物，進而利用鎳金屬作為末端炔自身偶合反應催化劑應用。 在攝氏50 度下，此三種配位基(La~c)可以與NiCl2 形成氮配位之雙金屬鎳錯合物[(Lx)Ni2Cl4(CH3OH)2] (x= a~c) (5a~5c)；藉由X 光單晶繞射分析儀器鑑定，顯示此系列鎳錯合物均為六配位的型態存在。並且加入三氟乙酸鈉，可以取代鎳雙金屬錯合物5a 的氯基團，從UV 吸收位移和IR 吸收及質譜可證實三氟乙酸根的配位。另外La~Lc，亦可以與[Cu(CH3CN)4PF6] 形成氮配位之雙金屬銅錯合物 [(Lx)Cu2(CH3CN)4]．2PF6 (x = a, b)，以丙酮和三氯甲烷混合溶劑條件下加熱，可得到以氯原子架接的雙銅錯合物[(Lx)Cu2Cl2] (x = a~c) (8a~c)。 另一方面，嘗試合成異核雙金屬錯合物，利用配位基(La)與當量的IrCl3．3H2O 在高溫下反應，可以得到氮配位銥金屬錯合物[[(La)Ir(H2O)Cl3]，藉由X 光單晶繞射分析儀器鑑定，顯示其為六配位單核銥金屬錯合物。 在催化應用探討上，測試雙鎳金屬錯合物(5a~5c)對於末端炔自身偶合反應的活性。發現錯合物5a 和5c 可以用氧氣做氧化劑，在溫和的條件(35oC)下，得到產率不錯的共軛炔基產物。
並列摘要
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).