多牙吡唑-萘啶配位基之金屬錯合物及其催化研究

Synthesis and Catalytic Application of Dimetal Complex with Pyrazolylnaphthyridine Ligand

蔡佳珉(Chia-Min Tsai)

指導教授 ： 劉緒宗

國立臺灣大學/理學院/化學研究所/碩士(2013年)

https://doi.org/10.6342/NTU.2013.11129

摘要

研究內容主要為合成2,7-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,8-naphthyridine (4)多牙氮配位基，以及其雙核銅和單核釕金屬錯合物，進而利用銅金屬錯合物作為末端炔自身偶合反應的催化劑。
在室溫下，配位基4可以與[Cu(CH3CN)4]PF6形成氮配位之雙銅金屬錯合物[(4)Cu2(CH3CN)4].2PF6 (5)，錯合物5可在氧氣環境中進一步合成銅二價雙銅金屬雙金屬錯合物[(4)Cu2(CH3COO)3(OH)] (11)。另外，此配位基亦可分別與CuBr、CuI在室溫下反應形成以鹵素為架橋配體的錯合物[(4)Cu2Br2] (6)和[(4)Cu2I2] (7)，藉由NMR與ESI-MASS鑑定其結構。配位基4亦用來合成釕金屬錯合物，在攝氏40度下，4與[Ru(benzene)Cl2]2反應可得到單釕金屬錯合物[(4)Ru(benzene)Cl2] (8)，藉由X光單晶繞射分析儀器鑑定，釕金屬中心為六配位的形態，同時以NMR與ESI-MASS進行分析，其數據皆與晶體資料相符。
雙銅錯合物可有效的作為末端炔自身偶合的催化劑。在鹼性環境中，雙銅錯合物5以氧氣作為氧化劑，在溫和的條件下，可得到產率不錯的共軛炔基產物，此外也與雙銅錯合物6、7以及銅二價雙金屬錯合物11進行反應性的比較。

關鍵字

雙銅錯合物

並列摘要

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.

並列關鍵字

Dinuclear Copper Complex

參考文獻

38. 廖倍偲 國立台灣大學化學系博士論文-金屬紫質與雙金屬錯合物之合成與其催化活性, 2012.

1. Finkbeiner, H. L.; Hay, A. S.; White, D. M. Polymerization Processes; Schildknecht, C. E., Skeist, I., Eds.; Wiley-Interscience: New York, 1977; pp 537.

3. Schindler, S. Eur. J. Inorg. Chem. 2000, 2311-2326.

6. van den Beuken, E. K.; Feringa, B. L. Tetrahedron 1998, 54, 12985-13011.

8. Rubino, J. T.; Franz, K. J. J. Inorg. Biochem. 2012, 107, 129-143.