資料載入中.....
|
請使用永久網址來引用或連結此文件:
http://ir.ncue.edu.tw/ir/handle/987654321/18945
|
| 題名: | Direct Arylation Mediated by Palladium Complexes with Rigid Phosphine-Functionalized N-Heterocyclic Carbenes |
| 作者: | Ho, Chien-Chang;Sandipan Chatterjee;Wu, Tzu-Liang;Chan, Kai-Ting;Chang, Yu-Wei;Hsiao, Tsun-Hung;Lee, Hon Man |
| 貢獻者: | 化學系 |
| 日期: | 2009-05
|
| 上傳時間: | 2014-08-14T04:29:35Z
|
| 出版者: | American Chemical Society |
| 摘要: | New phosphine-functionalized N-heterocyclic carbene ligand precursors (L1H·I and L2H·I) were prepared. The former compound contains a PPh2 moiety, whereas the latter one has a more electron-donating PCy2 group. A reaction of L1H···I with PdCl2 in the presence of base afforded the complex PdL1ClI. An interconversion process between the two structural isomers of PdL1ClI was observed by variable-temperature NMR. The coalescence temperature (Tc) is at 368 K with the free energy of activation (ΔG) found to be 68.9 kJ mol−1. A similar reaction of L2H·I with PdCl2 produced a mixture of PdL2ClI, PdL2Cl2, and PdL2I2. Unlike PdL1ClI, PdL2ClI undergoes a much faster exchange between the two structural isomers. Pure PdLI2 (L = L1 and L2) can be obtained by adding NaI in the reaction mixture to facilitate ligand exchange. [PdL(CH3CN)2](BF4)2 were also prepared straightforwardly by salt metathesis reactions. In total, seven new palladium complexes of L were structurally characterized, and in each of these structures an anagostic interaction exists between the palladium center and one of the diastereotopic methylene protons. The interaction also exists in solution, as evidenced by the downfield NMR shift of the proton. The new complexes PdLI2 and [PdL(CH3CN)2](BF4)2 show mediocre activities in benchmark Suzuki coupling reactions under conventional and microwave heating. They are, however, highly promising in mediating direct arylation of phenyl halides and diphenylacetylene, affording 9-benzylidene-9H-fluorene in good yields. |
| 關聯: | Organometallics, 28(9): 2837-2847 |
| 顯示於類別: | [化學系] 期刊論文
|
文件中的檔案:
| 檔案 |
大小 | 格式 | 瀏覽次數 |
|---|
| index.html | 0Kb | HTML | 587 | 檢視/開啟 |
|
在NCUEIR中所有的資料項目都受到原著作權保護.
|
