摘要
合成了两种新的簇合物(C_6H_5C≡CC_6H_4-Br-p)Co_2(CO)_(6-x)(PPh_3)_x(n=1,2),并用循环伏安法研究了一系列(RC≡CR’)Co_2(CO)_(6-x)L_x (n=0,1,2;L=PPh_3)和(RC≡CR’)Co_2(CO)_6与PPh_3在丙酮中的电化学行为.对于(RC≡CR’)Co_2(CO)_(6-x)L_x,其主要电极过程为(RC≡CR’)Co_2(CO)_(6-x)L_x+e(RC≡CR’)Co_2(CO)_(6-x)L_x^-此过程的还原电势E_p^(red)的大小与RC≡CR’及L有关.当C_2Co_2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.
Two new clusters (C6H5C2C6H4-Br-p)Co2(CO)6-R(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-nLR, their main electrode processes are as follows: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.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
1989年第10期1026-1029,共4页
Chemical Journal of Chinese Universities
基金
国家自然科学基金
关键词
钴簇合物
羰基
LEWIS碱
电催化反应
Cobalt, Carbonyl cluster, Lewis base, Synthesis, Cyclic voltammetry
