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/987654321/18920
|
題名: | Rhodium Complexes of PCNHCP Ligand: Oxidative Addition of Dichloromethane and Catalytic Hydrosilylation of Alkynes Affording (E)-Allenylsilanes |
作者: | Zeng, Jing-Yao;Hsieh, Meng-Hua;Lee, Hon Man |
貢獻者: | 化學系 |
日期: | 2005-12
|
上傳時間: | 2014-08-14T04:29:04Z
|
出版者: | Elsevier |
摘要: | New rhodium complexes of PCNHCP have been synthesized by using the silver transfer reagent, [Ag3(PCNHCP)2Cl]Cl2 (2). In the reaction between 2 and [Rh(COD)Cl]2 in dichloromethane, the presumably formed nucleophilic RhI(PCNHCP)Cl intermediate (A), undergoes a C–Cl bond activation of CH2Cl2 giving cis,mer-RhIII(PCNHCP)(CH2Cl)Cl2 (3) as the final product. Attempts to isolate A affords the oxidative degradation product of mer-RhIII(PCNHCP)Cl3 complex (4). In contrast, the rhodium(I) center in Rh(PCNHCP)(CO)Cl (5) is stabilized by the π-back bonding of CO ligand; a robust complex is, therefore, obtained. The solid-state structures of 2 and 3 were determined by X-ray diffraction. Complexes 3–5 are catalyst precursors for efficient, chemoselective hydrosilylation of alkynes. For the reaction between phenylacetylene and dimethylphenylsilane, a rapid hydrosilylation occurs, producing isomers of alkenylsilanes; then a slow isomerization pathway converts (Z)-alkenylsilane to its (E)-isomer. For 3, under catalytic condition, a facile reductive elimination of dichloromethane giving A is anticipated. The similarity in reactivity and selectivity between 3, 4 and 5 suggests the involvement of A as the active species in a common catalytic cycle. |
關聯: | Journal of Organometallic Chemistry, 690(24-25): 5662-5671 |
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 | 526 | 檢視/開啟 |
|
在NCUEIR中所有的資料項目都受到原著作權保護.
|