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Electrochemical Investigation of Redox Processes of Labile Cu(II)/Cu(I)-Cl Complexes by Scanning Electrochemical Microscopy.
Analytical Chemistry ( IF 7.4 ) Pub Date : 2020-07-05 , DOI: 10.1021/acs.analchem.0c00797
Yao Meng 1 , Jiahao Chen 1 , Kunjie Liang 1
Affiliation  

The studies reported here provide detailed information on the kinetics and reaction mechanism determined by the scanning electrochemical microscopy (SECM) for Cu(II)/Cu(I) redox reactions in a system with excess chloride. In positive feedback mode, the tip voltammograms obtained consist of two partially overlapping reduction waves, not one quasi-reversible process as was always thought. The reduced species of CuIICl42– and [CuIICl3(H2O)] could coexist during the time scale of SECM measurements, due to the slowness of the ligand substitution reaction of [CuIICl3(H2O)] to CuIICl42–. The stepwise EC reactions of CuIICl42– have experienced the same electron transfer kinetics as do outer-sphere reactants, while the reactions of [CuIICl3(H2O)] followed concerted EC pathways and much lower rate constants can be obtained, mainly due to the nonadiabatic character of electron transfer (k0Pt/k0Au = 1.625). The findings of this study can offer valuable insights for analyzing the electrode kinetics of labile complexes of metals in aqueous solutions.

中文翻译:

用扫描电化学显微镜对不稳定的Cu(II)/ Cu(I)-Cl配合物的氧化还原过程进行电化学研究。

此处报道的研究提供了有关在具有过量氯化物的系统中通过扫描电化学显微镜(SECM)确定的Cu(II)/ Cu(I)氧化还原反应的动力学和反应机理的详细信息。在正反馈模式下,获得的尖端伏安图由两个部分重叠的还原波组成,而不是像通常认为的那样是一个准可逆过程。在SECM测量的时间范围内,由于[Cu II Cl 3(H)的配体取代反应的缓慢,Cu II Cl 4 2–和[Cu II Cl 3(H 2 O)] -的还原物种可能共存。2 O)] -至Cu II Cl 4 2–。Cu II Cl 4 2–的逐步EC反应经历了与外层反应物相同的电子转移动力学,而[Cu II Cl 3(H 2 O)] -的反应遵循一致的EC途径和低得多的速率常数可以得到,主要是由于电子传递的非绝热特性(k 0 Pt / k 0 Au = 1.625)。这项研究的发现可以提供有价值的见解,以分析水溶液中金属的不稳定络合物的电极动力学。
更新日期:2020-08-04
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