Mechanism of dimerization of 1,4-dithiafulvenes into TTF vinylogues
Mechanism of dimerization of 1,4-dithiafulvenes into TTF vinylogues
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DOI：
10.1021/jp961048v
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发表时间：
1996-08-29
影响因子：
--
通讯作者：
Robert, A
中科院分区：
文献类型：
--
作者：
Hapiot, P;Lorcy, D;Robert, A
用循环伏安法研究了一系列取代的二硫代富瓦烯(DTF)在低和高扫描频率下氧化二聚生成四硫富瓦烯(TTF)的反应机理。它首先涉及阳离子自由基的形成，阳离子自由基偶联形成质子化的正离子。这个求积慢慢地去质子化，得到最终的TTf(k=0.5-1 S(-1))。二聚速率常数k(Dim)=(2-4)×10(8)L摩尔(-1)S(-1)，随取代基性质变化不大。
Mechanism of the oxidative dimerization of DTF (dithiafulvenes) to form TTF vinylogues (tetrathiafulvalenes) has been investigated by cyclic voltammetry at low and high scan rates for a series of substituted DTF. It involves first the formation of the cation radical which couples to form the protonated dication. This dication slowly deprotonates to give the final TTF (k=0.5-1 s(-1)). The dimerization rate constant was found to be in the range of k(dim)=(2-4) x 10(8) L mol(-1) s(-1) and not vary much with the nature of the substituent.