Mechanisms of electrochemically-induced retro-cyclopropanation reactions of fullerene derivatives using digital simulations
Mechanisms of electrochemically-induced retro-cyclopropanation reactions of fullerene derivatives using digital simulations
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DOI：
10.1002/chem.200204407
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发表时间：
2003-05-09
影响因子：
4.3
通讯作者：
Echegoyen, L
中科院分区：
文献类型：
--
作者：
Carano, M;Echegoyen, L
在高真空下，在无水四氢呋喃 (THF) 中，通过循环伏安法 (CV) 研究了三种 C-60 衍生物 1、2 和 3。 CV 行为基本上与其他环丙烷化富勒烯衍生物观察到的相似。在第二次还原过程之后，所有化合物都会发生化学反应，产生另一种电活性物质。这种“新”化学物质很可能是环丙烷环打开的化合物。观察到不同加数的 CV 行为存在差异。在给定电位窗口的不同扫描速率下获得的电化学数据与 BAS 数字模拟程序 DigiSim 相匹配。本研究的目的是探讨所提出的机制，并获得对 CV 实验期间发生的均相化学反应的动力学常数的可靠估计。 PM3 级别的计算为数字模拟得出的结论提供了额外的支持。所提出的机制对于所有化合物都是相似的，并且涉及可逆方形方案中的两个主要化学反应。
Three C-60 derivatives, 1, 2 and 3, have been studied by cyclic voltammetry (CV) under high vacuum in anhydrous tetrahydrofuran (THF). The CV behavior was essentially similar to that already observed for other cyclopropanated fullerene derivatives. After the second reduction processes all compounds undergo a chemical reaction that generates another electroactive species. This "new" chemical species is likely to be the compound with the cyclopropane ring open. Differences in CV behavior were observed for the different addends. Electrochemical data obtained at different scan rates for a given potential window, were fit with the BAS digital simulation program, DigiSim. The purpose of this study was to probe the proposed mechanisms and to obtain reliable estimations of the kinetic constants for the homogeneous chemical reactions taking place during the CV experiments. Calculations at the PM3 level lend additional support to the conclusions derived from digital simulations. The proposed mechanism is similar for all the compounds and involves two main chemical reactions in a reversible square scheme.