EXAMINATION OF CONDITIONS UNDER WHICH THE REDUCTION OF THE COBALTOCENIUM CATION CAN BE USED AS A STANDARD VOLTAMMETRIC REFERENCE PROCESS IN ORGANIC AND AQUEOUS SOLVENTS
EXAMINATION OF CONDITIONS UNDER WHICH THE REDUCTION OF THE COBALTOCENIUM CATION CAN BE USED AS A STANDARD VOLTAMMETRIC REFERENCE PROCESS IN ORGANIC AND AQUEOUS SOLVENTS
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DOI：
10.1021/ac00049a012
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发表时间：
1993-01-01
影响因子：
7.4
通讯作者：
BOND, AM
中科院分区：
文献类型：
--
作者：
STOJANOVIC, RS;BOND, AM
在非质子溶剂和质子溶剂中，在悬垂汞滴电极上，以及在各种半径的常规和微型铂、金和玻璃碳圆盘电极上，广泛地研究了还原钴镉离子作为六氟磷酸盐的两个单电子过程。在精心选择的条件下，Cc+/Cc0和Cc0/Cc-对（Cc =钴二烯）都可以用作可逆伏安参考系统。然而，Cc+/Cc0是首选的参考过程，因为非常负的电位和可能与溶剂响应重叠的问题有时会阻止Cc0/Cc-对作为实际的伏安参考系统使用。此外，计算出Cc+/Cc0体系的半波电位相对于广泛使用的Fc+/Fc参考对（Fc =二茂铁）为-1.35 +/- 0.01 V，并且相对于二茂铁参考电位基本上与电极材料、电解质和溶剂无关。相反，相对于二茂铁参考电位，Cc0/Cc-偶联的半波电位在很大程度上取决于溶剂的性质。
The two one-electron processes for reduction of the cobaltocenium cation as the hexafluorophosphate salt have been studied extensively in both aprotic and protic solvents at a hanging mercury drop electrode and at conventionally and microsized platinum, gold, and glassy carbon disk electrodes of various radii. Under carefully chosen conditions, both the Cc+/Cc0 and Cc0/Cc- couples (Cc = cobaltocene) can be used as reversible voltammetric reference systems. However, the Cc+/Cc0 couple is the preferred reference process since the combination of a very negative potential and possible overlap problems with the solvent response sometimes prevents the Cc0/Cc- couple from being used as a practical voltammetric reference system. Furthermore, the half-wave potential for the Cc+/Cc0 system was calculated to be -1.35 +/- 0.01 V vs the widely used Fc+/Fc reference couple (Fc = ferrocene) and is essentially independent of electrode material, electrolyte, and solvent relative to the ferrocene reference potential. In contrast,the half-wave potential for the Cc0/Cc- couple relative to the ferrocene reference potential is significantly dependent on the nature of the solvent.