含氮雜環碳烯一價銅金屬錯化合物的合成、鑑定與催化應用探討

Synthesis, Characterization and Catalytic Application of N-Heterocyclic Carbene Copper(I) Complexes.

潘慶豪(Ching-hao Pan)

指導教授 ： 于淑君

國立中正大學/理學院/化學暨生物化學系/碩士(2015年)

摘要

銅金屬在地殼中含量豐富，回收再使用的比例高，價格遠較其他貴金屬來得便宜，而且生物毒性低，可用於製造易回收的工業及民生用品，也是人體所需的微量金屬元素，具有多元的化學應用性，在二十世紀初期就被科學家當作觸媒使用。
我們成功的使用直接生成 (in situ) 的方式分別將咪唑 (imidazolium) 鹽類 (Pybim)HBr (2) 和 (Mesbim)HBr (4) 與叔丁醇鈉 (NaOtBu) 和一價銅溴化亞銅 (CuBr) 或 Cu(CH3CN)4PF6反應生成三種含氮雜環碳烯一價銅錯化合物 CuBr(Pybim) (6)，CuBr(Mesbim) (7) 與 [Cu(Pybim)2]PF6 (8)，並以核磁共振儀 (NMR)、原子吸收光譜儀 (AA)、紅外線光譜儀 (IR)、電噴灑離子化質譜儀 (ESI-Mass) 以及元素分析儀 (EA) 鑑定三種一價銅錯化合物的結構，綜合分析結果，我們確認一價銅錯化合物的結構，其中，一價銅錯化合物 6、7 為 NHC 配位基以一配位的方式與金屬鍵結，而一價銅錯化合物 8 則是NHC 配位基以二配位的方式與金屬鍵結。
本論文使用一價銅錯化合物 CuBr(Pybim) (6)、CuBr(Mesbim) (7) 與 [Cu(Pybim)2]PF6 (8) 作為觸媒催化 A3 偶和反應，以及催化合成 N-sulfonylamidines，除了傳統熱對流加熱方式外，並以微波促進催化反應，發現可以大幅減少催化反應時間，增加了能源使用效率，達到綠色化學的目標。

關鍵字

催化劑 ； 銅

並列摘要

Copper is an earth-abundant, inexpensive, high recycling rate and non-toxic metal element. It is the most common metals in industrial and daily necessities. In addition, it is essential to all living organisms as trace dietary minerals. Their chemistry as being catalysts has been established since at the turn of the twentieth century.
In this present study, three copper(I) complexes { CuBr(Pybim) (6), CuBr(Mesbim) (7) and [Cu(Pybim)2]PF6 (8)} were synthesized from direct reaction of imidazolium salts (Pybim)HBr (2) and (Mesbim)HBr (4) with CuBr or Cu(CH3CN)4PF6 in the presence of NaOtBu. The structure of copper(I) complexes 6, 7 and 8 were analyzed by using NMR, AA, IR, and ESI-mass. According to the analyzed data, we determined the compositions of copper(I) complexes, copper(I) complexes 6 and 7 were one ligand binding to copper and copper(I) complexes 8 was two ligand binding to copper.
We utilized copper(I) complexes { CuBr(Pybim) (6), CuBr(Mesbim) (7) and [Cu(Pybim)2]PF6 (8)} as catalysts to catalyze A3-coupling and synthesis of N-sulfonylamidines. Furthermore we used microwave flash heating conditions to promote catalysis reactions, in order to reduce reaction time, increase the efficiency of reactions and reach the goal of green chemistry.

並列關鍵字

Copper ； Catalyst

參考文獻

(1) International Copper Association.

(2) International Copper Study Group.

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(7) Weingarten, H. J. Org. Chem. 1964, 29, 3624.