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Electron transfer and structural change: Distinguishing concerted and two-step processes

机译:电子转移与结构变化:区分一致的过程和两步过程

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In electron-transfer reactions accompanied by structural changes, the structural change can be concerted with electron transfer or can occur in a separate reaction either preceding or following the electron-transfer step. In this paper we discuss ways of distinguishing concerted reactions from the latter two-step type. Included are recent examples in which no intermediates have been detected in the reactions, thus precluding the direct assignment to the two-step category. In these cases, other means are used to build support for the two-step mechanism with respect to the concerted process. These include an example of structural change preceding electron transfer, a demonstration that the current models of concerted reactions cannot fit the voltammetric data, and a case in which an independent measure of the inner reorganization energy was used to show that the reaction could not be a concerted electron transfer and structural change.
机译:在伴随结构改变的电子转移反应中,结构改变可以与电子转移一致,或者可以在电子转移步骤之前或之后的单独反应中发生。在本文中,我们讨论了区分协调反应和后两步反应类型的方法。包括最近的实例,其中在反应中未检测到任何中间体,因此排除了直接分配给两步法类别的可能性。在这些情况下,就协调过程而言,还可以使用其他方式为两步机制建立支持。这些包括电子转移前结构变化的例子,当前的协同反应模型无法拟合伏安数据的证明,以及使用内部重组能的独立度量来表明反应不可能是伏安法的情况。协调的电子转移和结构变化。

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