Electron-transfer reactions of aromatic radical ions with nucleophilic molecules

Electron-transfer reactions of aromatic radical ions with nucleophilic molecules
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芳香族自由基离子与亲核分子的电子转移反应

DOI:
10.1039/ft9928800195
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发表时间:
1992
期刊:
影响因子:
--
通讯作者:
J. K. Thomas
J. K. Thomas
中科院分区:
--
文献类型:
--
作者:
K. Koike;J. K. Thomas

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芘、蒽和苯并菲自由基阳离子与富电子物种的反应已被确定为自然界中的电子转移。这些体系的反应速率是由扩散过程中的碰撞控制的,而不是由电荷转移络合物等中间体的形成控制的,从供体分子到Py,An,Tr自由基阳离子的电子转移速率在-1.7 <$ΔG <$0.2范围内没有明显的降低。利用量子力学Marcus能隙定律,在电子-隧穿相互作用具有较大耦合常数的情况下,模拟了kET与ΔG的关系.
Reactions of pyrene, anthracene and triphenylene radical cations with electron-rich species have been established as being electron transfer in nature. The reaction rates of these systems were controlled by collision through diffusional processes rather than by formation of an intermediate such as a charge-transfer complex.Electron-transfer rates from the donor molecules to Py, An, Tr radical cations did not show significant decrease in the range –1.7 ⩽ΔG⩽ 0.2. The ΔG dependence of kET was simulated by using the quantum mechanical Marcus' energy-gap law with a relatively large coupling constant value for the electron-tunnelling interaction.