Mechanistic discrimination of the reaction of 1-aminopyrene cation radical using an electron transfer stopped-flow method. Decay reaction accelerated by neutral molecules
Mechanistic discrimination of the reaction of 1-aminopyrene cation radical using an electron transfer stopped-flow method. Decay reaction accelerated by neutral molecules
复制标题
使用电子转移停流法对 1-氨基芘阳离子自由基的反应进行机理判别。
DOI：
10.1016/s1388-2481(01)00183-7
复制
发表时间：
2001
期刊：
影响因子：
--
通讯作者：
S. Okazaki
中科院分区：
文献类型：
--
作者：
M. Oyama;T. Higuchi;S. Okazaki
采用电子转移停流（ETSF）方法，研究了1-氨基芘阳离子自由基（AP+）在乙腈中的衰变动力学。当AP+通过与三(对溴苯基)胺(TBPA)阳离子自由基的电子转移定量形成时，发现衰变反应按照-d[AP+]/dt=k[AP+]2的速率定律进行，表明阳离子自由基-阳离子自由基耦合(RRC)机制。相比之下，在AP存在下，衰变反应显着加速，动力学发生变化，遵循-d[AP+]/dt=k[AP+]2[AP]的速率定律，这表明两步相互作用如下：导电高分子材料。 ETSF 方法可以阐明中性分子对阳离子自由基反应动力学的影响，而使用电化学技术很难揭示这一影响。
Using an electron transfer stopped-flow (ETSF) method, the decay kinetics of 1-aminopyrene cation radical (AP+) in acetonitrile was studied. When AP+was formed quantitatively via the electron transfer with tris(p-bromophenyl)amine (TBPA) cation radical, it was found that the decay reaction proceeded according to a rate law of −d[AP+]/dt=k[AP+]2, indicating the cation radical–cation radical coupling (RRC) mechanism. In contrast, in the presence of AP, the decay reaction was accelerated remarkably, and the kinetics has been changed to adhere to a rate law of −d[AP+]/dt=k[AP+]2[AP], which indicated the two step interactions as follows: [Formula: see text] While the reactions of aromatic amine cation radicals have been revealed as the RRC mechanism mainly, the present type of interaction can be regarded as a possible reaction mechanism of cation radicals, and would be important to control the formation of conducting polymer materials. The ETSF method has permitted the clarification of the effect of the neutral molecules on the reaction kinetics of cation radicals, which would be very difficult to reveal using electrochemical techniques.