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Electrochemical and electron transfer behavior of o-chloranil with the presence of Mg2+ in acetonitrile

机译：Mg2 +在乙腈中存在的邻氯甲腈的电化学和电子转移行为

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摘要

The reduction process of o-chloranil (o-CA) with the presence of Mg2+ was observed in acetonitrile on a platinum electrode to compare that of p-chloranil (p-CA) with Mg2+. Although the reduction potentials of o-CA and p-CA were not so different without Mg2+, apparent differences were recognized for both reduction processes in the presence of Mg2+. While the adsorption of a Mg2+ salt of p-CA dianion, Mg(2+)p-CA(2-), was reported, no adsorption of the reduced forms of o-CA was observed. Alternatively, significant changes in the electrochemical responses were observed implying a rigid complexation between Mg2+ and o-CA(2-) in solution. In addition, using a stopped-flow technique, the occurrence of the electron transfer between ferrocene, whose formal oxidation potential is +0.26 V (vs. I-3(-), I-), and o-CA, whose formal reduction potential is 0.00 V, was observed in the presence of Mg2+, though the Spontaneous electron transfer did not occur without Mg2+. This indicates the effect of Mg2+ to make the redox potential of o-CA positive by complexing, while this is not the case of p-CA. [References: 15]
机译：在铂电极上的乙腈中观察到了存在Mg2 +的邻氯苯胺（o-CA）的还原过程，以比较对氯苯胺（p-CA）与Mg2 +的还原过程。尽管在没有Mg2 +的情况下，o-CA和p-CA的还原电位没有太大差异，但是在存在Mg2 +的情况下，两种还原过程均存在明显差异。虽然据报道吸附了p-CA二价阴离子的Mg2 +盐Mg（2+）p-CA（2-），但未观察到还原形式的o-CA的吸附。另外，观察到电化学反应的显着变化，这意味着溶液中Mg2 +和o-CA（2-）之间存在刚性络合。此外，使用停止流技术，在形式氧化电位为+0.26 V（vs. I-3（-），I-）的二茂铁与形式还原电位为o-CA之间发生电子转移在存在Mg2 +时观察到的是0.00 V，尽管没有Mg2 +时不会发生自发电子转移。这表明Mg2 +通过络合使o-CA的氧化还原电位为正的作用，而p-CA并非如此。 [参考：15]

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