Alkyl and Aryl Substituted Corroles. 1. Synthesis and Characterization of Free Base and Cobalt Containing Derivatives. X-ray Structure of (Me4Ph5Cor)Co(py)2
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- 作者：Roger Guilard ; Claude P. Gros ; Fré ; dé ; ric Bolze ; Franç ; ois Jé ; rô ; me ; Zhongping Ou ; Jianguo Shao ; Jean Fischer ; Raymond Weiss ; and Karl M. Kadish
- 刊名：Inorganic Chemistry
- 出版年：2001
- 出版时间：September 10, 2001
- 年：2001
- 卷：40
- 期：19
- 页码：4845 - 4855
- 全文大小：176K
- 年卷期：v.40,no.19(September 10, 2001)
- ISSN：1520-510X
文摘
The synthesis, spectroscopic properties, and electrochemistry of six different alkyl- and aryl-substituted Co(III)corroles are presented. The investigated compounds contain methyl, ethyl, phenyl, or substituted phenyl groupsat the eight 
-positions of the corrole macrocycle and four derivatives also contain a phenyl group at the 10-mesoposition of the macrocycle. Each cobalt corrole undergoes four reversible oxidations in CH2Cl2 containing 0.1 Mtetra-n-butylammonium perchlorate and exists as a dimer in its singly and doubly oxidized forms. The differencein potential between the first two oxidations is associated with the degree of interaction between the two corroleunits of the dimer and ranges from an upper value of 0.62 V, in the case of (Me6Et2Cor)Co, to a lower value ofabout 0.17 V, in the case of four compounds which have a phenyl group located at the 10-meso position of themacrocycle. These Co(III) corroles strongly coordinate two pyridine molecules or one carbon monoxide moleculein CH2Cl2 media, and ligand binding constants were evaluated using spectroscopic and electrochemical methods.The structure of (Me4Ph5Cor)Co(py)2 was also determined by X-ray diffraction. Crystal data: (Me4Ph5Cor)Co(py)2·3CH2Cl2·H2O, orthorhombic, a = 19.5690(4) Å, b = 17.1070(6) Å, c = 15.9160(6) Å, V = 5328.2(5) Å3,space group Pna21, Z = 2, 35 460 observations, R(F) = 0.069.
-positions of the corrole macrocycle and four derivatives also contain a phenyl group at the 10-mesoposition of the macrocycle. Each cobalt corrole undergoes four reversible oxidations in CH2Cl2 containing 0.1 Mtetra-n-butylammonium perchlorate and exists as a dimer in its singly and doubly oxidized forms. The differencein potential between the first two oxidations is associated with the degree of interaction between the two corroleunits of the dimer and ranges from an upper value of 0.62 V, in the case of (Me6Et2Cor)Co, to a lower value ofabout 0.17 V, in the case of four compounds which have a phenyl group located at the 10-meso position of themacrocycle. These Co(III) corroles strongly coordinate two pyridine molecules or one carbon monoxide moleculein CH2Cl2 media, and ligand binding constants were evaluated using spectroscopic and electrochemical methods.The structure of (Me4Ph5Cor)Co(py)2 was also determined by X-ray diffraction. Crystal data: (Me4Ph5Cor)Co(py)2·3CH2Cl2·H2O, orthorhombic, a = 19.5690(4) Å, b = 17.1070(6) Å, c = 15.9160(6) Å, V = 5328.2(5) Å3,space group Pna21, Z = 2, 35 460 observations, R(F) = 0.069.© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |