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題 名 | Identification and Characterization of CB-PAO Diastereoisomers of Technetium (v) Complexes by Using NMR Spectroscopy Method=以核磁共振光譜法鑑別鎝氧六甲基丙烯胺肟非鏡像立體異構物之研究 |
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作 者 | 蔡長書; | 書刊名 | 慈濟技術學院學報 |
卷 期 | 4 2002.08[民91.08] |
頁 次 | 頁127-147 |
分類號 | 418.346 |
關鍵詞 | 核磁共振; 非鏡像立體異構物; 鎝錯合物; 非化學等價; Nuclear magnetic resonance; NMR; Diastereoisomer; Technetium complex; Chemical non-equivalence; |
語 文 | 英文(English) |
中文摘要 | 由1H-NMR及13C-NMR光譜圖知,僅有13C-NMR可以分辨d,l-型和meso-型CB-PAO配位子,因為就環丁烯基上的三個甲烯基而言,由於meso-型分子的對稱結果,形成三個13C-NMR訊號分別為δ15.18(CrH2),δ28.18(Cα,H2)以及δ28.28(CβH2),而d,l-型卻只產生兩個訊號分別為δ15.18(CrH2),δ28.11(Cα,βH2)。此外,d,l-CBPAO有8組碳種類,而meso-CB-PAO則有9組,亦可明顯鑑別不同種類立體異構物。 就99TcO-d,l-CBPAO之1H-NMR光譜圖而言,在不對稱碳上的兩個氫原子(bH; jH) 其與鎝氧核上的氧以及另一個不對稱碳上的甲基(iCH3, CCH3)所形成之立體化學環境不相同,彼此屬於非化學不等價,故受甲基上三個氫原子影響而分裂為兩個四重峰。就99TcO-meso-CB-PAO而言,bH與jH,對鎝氧核上的氧及相關之iCH3及CCH3甲基所形成之立體化學環境相同,彼此屬於化學等價,因此受甲基上三個氫原子分裂為一個四重峰。此外,就99TcO-d,l-CBPAO 之CH2N上的四個氫原子(2dH,2hH)而言,其所處鎝氧核上的氧及不對稱碳上的甲基之立體化學環境皆不相同,屬於化學不等價,故受同一碳上的另一氫原子影響,分裂為四個二重峰,然而,對於99TcO-meso-CB-PAO而言,接在同一碳上的兩個氫原子,屬於非化學不等價,但其各別卻又和另一碳上的兩個氫原子分別屬於化學不等價,因而受到同一碳上另一氫原子影響,只分裂為兩個二重峰。就13C-NMR光譜顯示99Tc-d,l-CB-PAO有12組不同環境之碳種類,而99Tc-meso-CB-PAO只有9組,根據上述實驗結果,以核磁共振光譜法可有效鑑別及確認d,l-CB-PAO與meso-CB-PAO非鏡像立體異構之鎝錯合物。 |
英文摘要 | 13C-NMR spectroscopy is only suitable to identify the stereochemical isomers of CB-PAO due to the different NMR signals of –CH2- on the same cyclobutyl group. Because of the symmetry of meso-form molecular structure, it appears three 13C-NMR signal on δ15.18 (CrH2),δ28.18(Cα,H2) and δ28.28(CβH2) for meso-CB-PAO. However, it appears just only two 13C-NMR signal onδ15.18(CrH2),δ28.11(Cα,βH2) for d,l-CB-PAO. In addition, 13C-NMR spectroscopy of meso-CB-PAO displays nine kinds of carbon type, but that of d,l-CB-PAO displays only eight kinds of C type. For 99TcO-d,l-CB-PAO complex, the stereochemical environments on the unsymmetrical carbon are different between two H(bH,jH);O (Tc=O) and methyl group (iCH3; cCH3). They are belong to chemical non-equivalence and splitted into two quartet on the influence of three hydrogen atoms. For 99Tc-meso-CB-PAO complex, they are belong to chemical equivalence and splitted into one quartet. For 99TcO-d,l-CB-PAO complex, the stereochemical environment of the four hydrogen (2dH, 2hH) on –CH2N- group is different between oxygen (Tc=O) and methyl (unsymmetrical carbon). They are belong to chemical non-equivalence and splitted into four doublet. For 99TcO-meso-CB-PAO complex, the two hydrogen on the same carbon are belong to chemical non-equivalence and splitted into two doublet. 13C-NMR measurements on 99TcO-d,l-CB-PAO complex displays 12 kinds of different environment of carbon types. However, it provides only 9 kinds of carbon types for 99TcO-meso-CB-PAO complex. According to the results of NMR spectroscopy, it is qualitatively feasible for the identification and characterization of CB-PAO diastereoisomers of technetium complexes. |
本系統中英文摘要資訊取自各篇刊載內容。