高等学校化学学报

高等学校化学学报 ›› 1989, Vol. 10 ›› Issue (10): 1026.

• 研究论文 • 上一篇    下一篇

(RC2R')Co2(CO)6及其与Lewis碱反应的电化学研究

孟庆金, 孙守恒, 步修仁, 游效曾   

  1. 南京大学配位化学研究所
  • 收稿日期:1988-02-23 出版日期:1989-10-24 发布日期:1989-10-24
  • 通讯作者: 游效曾
  • 基金资助:

    国家自然科学基金

Electrochemical Study of (RC2R')Co2(CO)6 and Their Reaction with Lewis Base

Meng Qingjin, Sun Shouheng, Bu Xiuren, You Xiaozeng   

  1. Coordination Chemistry Institute, Nanjing University, Nanjing
  • Received:1988-02-23 Online:1989-10-24 Published:1989-10-24

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摘要： 合成了两种新的簇合物(C6H5C≡CC6H4-Br-p)Co2(CO)6-x(PPh3)x(n=1,2),并用循环伏安法研究了一系列(RC≡CR')Co2(CO)6-xLx(n=0,1,2;L=PPh3)和(RC≡CR')Co2(CO)6与PPh3在丙酮中的电化学行为.对于(RC≡CR')Co2(CO)6-xLx,其主要电极过程为(RC≡CR')Co2(CO)6-xLx+e(RC≡CR')Co2(CO)6-xLx-此过程的还原电势Epred的大小与RC≡CR'及L有关.当C2Co2骨架上的电荷密度增大时,簇合物难被还原,却易被氧化.说明簇合物的前线分子轨道的能级既与钴有关,也与配体有关.簇合物得到一个电子形成的自由基是电子迁移催化反应的催化剂.

关键词: 钴, 羰基簇合物, Lewis碱, 合成, 循环伏安

Abstract: Two new clusters (C6H5C2C6H4-Br-p)Co2(CO)6-n(PPh3)n(n= 1,2) were synthesized.The electrochemical behavior of a series of (RC2R')Co2(CO)6-nLn(n=0,1,2;L = PPh3) and (RC2R').Co2(CO)6 in the presence of PPh3were studied in acetone by utilizing cyclic voltammetry.For (RC2R')Co2(CO)6-nLn, their main electrode processes are as follows:(RC2R')Co2(CO)6-n, Ln+e=(RC2R')Co2(CO)6-n, Ln-The reduction potential of this process is related to both RC2R' and L.The larger the charg density in C2Co2, the more difficultly by the cluster is to be reduced and the easier to be oxidized, which indicates that the energy level of frontier molecular orbital of cluster is related to both cobalt and ligand.The cluster radical is a catalyst for electron transferred catalyzed (ETC) reaction.

Key words: Cobalt, Carbonyl cluster, Lewis base, Synthesis, Cyclic voltammetry

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