分子诱导的基同解与二氧化
A A Fokin1, B A Tkachenko, O I Korshunov
1Department of Organic Chemistry, Kiev Polytechnic Institute, 37 Pobeda Avenue, 03056 Kiev, Ukraine.
Journal of the American Chemical Society
|November 8, 2001
概括
甲基二氧化 (DMD) 促进了推进剂中C-H和C-C键的激活. 这项研究揭示了第一个分子诱导的同解C-C键裂变,并详细介绍了C-H键氧化机制.
科学领域:
- 有机化学 有机化学
- 计算化学的计算化学
- 反应机制 反应机制
背景情况:
- 螺旋是一种具有独特反应性的应变多环碳化合物.
- 了解C-H和C-C键激活对于合成化学至关重要.
- 甲基二氧化 (DMD) 是一种强大的但有选择性的氧化剂.
研究的目的:
- 为了研究DMD在推进剂中激活C-H和C-C键的机制.
- 为了比较不同螺旋与DMD和氧化 (CrO2Cl2) 的反应性.
- 阐明这些激活过程的能量概况和途径.
主要方法:
- 实验研究与密度函数理论 (DFT) 计算相结合.
- 使用了B3LYP/6-311+G**//B3LYP/6-31G*的理论水平.
- 研究了3,6-脱荷马丹丹 (2) 和1,3-脱阿丹丹 (3) 与DMD和CrO2Cl2.2.的反应.
主要成果:
- 用DMD激活1,3-脱胺 (3) 的sigma(C-C) 激活是分子诱导的同解C-C键裂变的第一个例子.
- 3,6 - 脱荷荷马丹 (2) 与DMD的C-H键基化具有高度的强力作用,并通过协调的途径进行.
- 与DMD和CrO2Cl2的反应性模式显示出高度反应性的推进剂的并行性,但对于更稳定的推进剂则有所不同.
结论:
- 在推进剂中,DMD表现出不同的C-H和C-C键激活机制.
- 这项研究提供了对紧张系统中控制键激活的因素的宝贵见解.
- 计算和实验数据提供了对推进器反应性的全面了解.
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