| 摘要註: |
含雙氮雜環碳烯之咔唑配位基與醋酸鎳進行錯化反應，可形成醋酸根鎳金屬錯化合物。在氧氣下有機腈和鹼會與此錯化合物反應，切斷氰基烷的碳-氰鍵而形成氰基鎳金屬錯化合物。利用GC-FID, HPLC與LC-MS分析反應後產物發現含有benzaldehyde, benzoic acid, butyl benzoate, benzil和3-oxo-2,3-diphenylpropanenitrile，由此探討碳-氰鍵斷裂的可能反應機制。另外，合成含氮雜環四氫咔唑配位基6-methyl-8-(3-methylimidazolium-1-yl)-1,2,3,4-tetrahydrocarbazole diiodide, 8-(3-butylimidazolium-1-yl)-6-methyl-1,2,3,4-tetrahydrocarbazole dibromide和8-(3-benzylimidazolium-1-yl)-6-methyl-1,2,3,4-tetrahydrocarbazole dibromide，並以1H及13C核磁共振光譜、X-ray單晶繞射、元素分析與高解析質譜鑑定其結構與分子量。此類配位基與醋酸鎳進行錯化反應所得產物在1H核磁共振光譜為順磁性化合物，推測可能是三配位的鎳金屬錯化合物。 1,8-bis(N-heterocyclic carbene) carbazolide ligands react with Ni(OAc)2·4H2O to yield 1,8-bis(N-heterocyclic carbene) carbazolide acetate complexes. Under aerobic condition, reaction of these nickel complexes and organonitriles give nickel cyano compounds. GC-FID, HPLC and LC-MS analysis show the products containing benzaldehyde, benzoic acid, butyl benzoate, benzil and 3-oxo-2,3-diphenylpropanenitrile, which provide useful information for the mechanism of C-CN bond activation. Moreover, 6-methyl-8-(3-methylimidazolium-1-yl)-1,2,3,4-tetrahydrocarbazole diiodide, 8-(3-butylimidazolium-1-yl)-6-methyl-1,2,3,4-tetrahydrocarbazole dibromide and 8-(3-benzylimidazolium-1-yl)-6-methyl-1,2,3,4-tetrahydrocarbazole dibromide are prepared and characterized by 1H NMR, 13C NMR, X-ray diffraction, elemental analysis, and HRMS. Complexation of the above ligands and nickel acetate gives paramagnetic compounds, which might result from the three-coordinate feature of the metal central atom. |