在双二硫化物中的分子内电子转移
Gabriel B Hall1, Rudresha Kottani, Greg A N Felton
1Department of Chemistry and Biochemistry, The University of Arizona , P.O. Box 210041, Tucson, Arizona 85721, United States.
Journal of the American Chemical Society
|February 18, 2014
概括
减少性裂变的二硫化键可以直接发生,也可以通过分子内介导. 一个双二烯部分提供了通过分子内电子转移减少二硫化物键的低能途径.
科学领域:
- 电化学 电化学 电化学
- 有机化学 有机化学
- 生物化学 生物化学
背景情况:
- 在生物和化学系统中,二硫化物键的减少性裂变至关重要.
- 了解机制 (逐步与协同的电子转移) 和电子源 (分子间与分子内) 是关键.
研究的目的:
- 调查4,4'-双-3,3'-二硫化物 (1) 和其二-N-甲基化衍生物 (2(2+)) 的电化学还原机制.
- 阐明氧化还原活性部分在促进二硫化物键裂解中的作用.
主要方法:
- 循环电压测量在酸中.
- 密度函数理论 (DFT) 的计算.
- 电化学数据的模拟.
主要成果:
- 化合物1显示了直接的二硫化物还原,在第一和第二个电子转移之间存在很大的潜在差距.
- 化合物2 ((2+) 在较少负电位的双二部分被减少.
- 在2(2+) 中的二二的第二次减少触发了分子内电子转移,从而分裂了二硫化键.
结论:
- 化合物2 ((2+) 中的氧化还原活性比比里迪尼部分为二硫化物键的还原性裂解提供了一种高效的低能途径.
- 这种分子内机制绕过了直接二硫化物还原所需的高负潜力.
- 这项研究阐明了基于分子结构的二硫化物键减少的独特机制.
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