雙核金屬錯合物的合成和催化應用

Dinuclear Complexes-Synthesis and Catalytic Application

蘇子傑(Tzu-Chieh Su)

指導教授 ： 劉緒宗

國立臺灣大學/理學院/化學研究所/碩士(2012年)

https://doi.org/10.6342/NTU.2012.02861

摘要

本篇論文探討多牙氮配位基2,7-bi(2-pyridyl)-1,8-naphthyridine (bpnp)與錸金屬形成單核和雙核金屬錯合物，另以單核錸金屬錯合物與銥或鈀金屬進行螯合，形成兩種不同的異核金屬錯合物。雙錸金屬錯合物則探討氧氣的活化反應以及末端炔插入ethyl acetoacetate反應的催化劑。
在高溫下，bpnp會與Re2(CO)8(CH3CN)2形成氮-氮配位的單錸錯合物[N,N-Re(CO)3Cl(bpnp)](5a)和萘啶3號位進行碳-氫活化生成雙錸錯合物[N,N-Re(CO)3Cl(bpnp)(CO)4Re-C,N] (5b)。兩個錯合物均藉由NMR光譜與X光單晶繞射分析鑑定後其結構。單錸錯合物也可以與銥及鈀金屬在相同位置進行類似反應，藉由NMR光譜可證實在相同位置反應。
雙錸金屬錯合物利用照光活化，可以使氧氣活化將cyclohexadiene氧化成苯環產物。化合物5b可以催化末端炔插入ethyl acetoacetate 中α-s位的碳-碳鍵後生成δ-keto ester；此催化劑的使用可以讓該反應減短時間、減少催化劑的用量並且不需要加入4A分子篩，就可以達到相同的效果。

關鍵字

錸

並列摘要

We have successfully prepared and characterized mononuclear and dinuclear rhenium complexes containing 2,7-bi(2-pyridyl)-1,8-naphthyridine (bpnp) in this thesis. Treatment of Re2(CO)8(CH3CN)2 with bpnp under high temperature conditions provided mononuclear rhenium complex [N,N-Re(CO)3Cl(bpnp)] (5a).Further reaction of 5a with rhenium carbonyls resulted the o-metallation product [N,N-Re(CO)3Cl(bpnp)(CO)4Re-C,N] (5b). Similar C-H activations of 5a with (COD)PdCl2 and [(COD)IrCl]2 were also investigated. All complexes were characterized by spectroscopic methods such as NMR and Mass. Both structures of rhenium complexes 5a and 5b were further confirmed by X-ray crystallography.
With the exposure of light at 350 nm, dirhenium complex 5b catalyzed the aromatization of cyclohexadiene into benzene in the presence of oxygen. Futhermore, Complex 5b promoted the insert terminal alkyne into ethyl acetoacetates leading to δ-keto ester product, which then underwent cyclization to form 2-pyranones. His method provides a practical protocol for the preparation of 2-pyranones with less catalyst loading and reaction time.

並列關鍵字

rhenium

參考文獻

17. 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應用, 2011, 55.

19. Yang, F. M.; Chen, P. Y.; Lee, C. C.; Liu, Y. H.; Peng, S. M.; Chou, P. T.; Liu, S. T. Dalton Trans. 2012, 41, 5782-5784.

50. (a)Abdel-Shafi, A.A.; Bourdelabde, J.L.; Ali, S.S. Dalton Trans. 2007, 24, 2510-2516 (b)Jiang, G.; Chen, J.; Huang, J. S.; Che, C. M. Org. Lett. 2009, 11, 4568-4571.

1. Gavrilova, A. L.; Bosnich, B. Chem. Rev. 2004, 104, 349-383

8. Evens, G.; Caluwe, P. Macromolecule 1979, 12, 803-808.