生物启发的二硫化物/二硫化物再氧化开关在复合体中作为质子,H原子和化物转移反应剂
Shao-An Hua1, Lucas A Paul1, Manuel Oelschlegel1
1Universität Göttingen, Institut für Anorganische Chemie, Tammannstraße 4, D-37077 Göttingen, Germany.
Journal of the American Chemical Society
|April 16, 2021
概括
这项研究探讨了一种含有二硫化物/二硫化物部分的复合物,模仿质子合电子转移 (PCET) 的生物辅因子. 该复合体表现出多功能PCET反应性,释放出质子,原子或化离子.
科学领域:
- 协调化学 协调化学
- 电化学 电化学 电化学
- 生物有机化学 生物有机化学
背景情况:
- 质子合电子转移 (PCET) 在生物和化学反应中至关重要.
- 自然的氧化还原活性共因子启发了合成PCET试剂.
- 双硫化物/二硫化物对是显著的生物氧化还原系统.
研究的目的:
- 为了研究合成复合物的质子合电子转移 (PCET) 反应性.
- 为了探索独特的SH···-S小部分在双氨酸连接体中的作用.
- 模仿生物氧化还原活性共因子的功能.
主要方法:
- 一个复合物的合成,fac-[Re(S-Sbpy) ((CO) 3Cl].
- 用电化学方法将二硫化物键降低到一个dithiolate.
- 对dithiolate物种的质子化和随后的反应性的表征.
主要成果:
- 复合体在 -1.16 V 与 Fc 之间经历了两电子的减小,形成了滴氧酸盐物种.
- 滴叶酸的质子化形成了一个S-H···-S单元,pKa为24.7.
- 二硫化物/二硫醇系统表现出多样化的PCET反应性,释放H+ ,H原子或H- .
结论:
- 合成的复合物有效地模仿生物氧化还原因子.
- 二硫化物/二硫化物部分使得多功能质子合电子转移通路成为可能.
- 该系统为开发新的合成PCET试剂提供了一个平台.
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