頁籤選單縮合
題名 | Electron Transfer Chain Catalysis=電子移轉鏈觸媒反應 |
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作者 | 劉陵崗; Liu, Ling-kang; |
期刊 | 中央研究院化學研究所集刊 |
出版日期 | 19990600 |
卷期 | 46 1999.06[民88.06] |
頁次 | 頁31-39 |
分類號 | 346.01 |
語文 | eng |
關鍵詞 | Electron transfer chain catalysis; |
英文摘要 | Electron-transfer chain (ETC) catalysis belongs to the family of chain reactions where the electron is the catalyst. Pioneered by Prof. Taube in inorganic chemistry, the ETC catalysis is applied to the preparation of organometallic complexes, utilizing the greatly enhanced reactivity of organometallic 17e and 19e radicals. An electron transfer step followed by the "chemical propagation" and the "cross electron-transfer" steps, results in the overall reaction without net redox change. Applications to three ligand exchange reactions are discussed: (a) After a chemical initiation, the PR�� replacement selectively for l�� on (η��-C�Ε��) Fe (CO) �疹 follows the 17e-19e pathway that instantaneously gives [(η��-C�Ε��) Fe (CO)��(PPh��)�吞[l�涘. (b) Taking the advantage of radical pathway, the PPh�a Py�婀��a replacement for PPh�� on [( η�� -C�Ε��) Fe (CO) �烈Ph���吞 could establish the equilibrium rapidly. The slight differences in the donor capability of PPh�a Py�婀��a (n=0-3) are measured accordingly. (c) With a mixture of (η��-C�Ε��) Fe (CO)�疹 and excess P (OMe)�� and a catalytic amount of reductant, an ETC catalysis of two-levels has been observed on the P (OMe)�� substitution reactions at the first stage for l�� on (η��-C�Ε��) Fe (CO)�疹 and at the second stage for CO on [(η��-C�Ε��) Fe(CO) �� P (OMe)���吞. |
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