Chemistry of Cobalt Acetate. 7. Electrochemical Oxidation of 3-Oxo-Centered Cobalt(III) Acetate Trimers
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- 作者：James K. Beattie ; Corina U. Beck ; Peter A. Lay ; and Anthony F. Masters
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：December 15, 2003
- 年：2003
- 卷：42
- 期：25
- 页码：8366 - 8370
- 全文大小：106K
- 年卷期：v.42,no.25(December 15, 2003)
- ISSN：1520-510X
文摘
Electrochemical and spectroelectrochemical properties of five cobalt(III) acetate complexes [CoIII3(
3-O)(CH3CO2)5(OR)(py)3][PF6] are described, where py = pyridine and R = OCCH3 (A), H (B), CH3 (C), CH2CH=CH2 (D),and CH2C6H5 (E). Each is reduced irreversibly as observed by cyclic voltammetry at room temperature and at-40 
C in acetonitrile at scan rates up to 20 V s-1, but oxidized reversibly to a mixed-valence Co(III)2Co(IV)species at ~1.23 V vs the ferrocenium/ferrocene couple. Controlled potential coulometry confirmed a one-electron-oxidation process. Spectroelectrochemical oxidation of A at 5 C showed isosbestic points in the electronic absorptionspectrum that showed the oxidized complex to be stable in solution for at least 1 h.
3-O)(CH3CO2)5(OR)(py)3][PF6] are described, where py = pyridine and R = OCCH3 (A), H (B), CH3 (C), CH2CH=CH2 (D),and CH2C6H5 (E). Each is reduced irreversibly as observed by cyclic voltammetry at room temperature and at-40 C in acetonitrile at scan rates up to 20 V s-1, but oxidized reversibly to a mixed-valence Co(III)2Co(IV)species at ~1.23 V vs the ferrocenium/ferrocene couple. Controlled potential coulometry confirmed a one-electron-oxidation process. Spectroelectrochemical oxidation of A at 5 C showed isosbestic points in the electronic absorptionspectrum that showed the oxidized complex to be stable in solution for at least 1 h.