二氧化碳和甲的连续气相激活:事件的顺序很重要!
Shaodong Zhou1, Jilai Li1,2, Marjan Firouzbakht1
1Institut für Chemie, Technische Universität Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.
Journal of the American Chemical Society
|April 14, 2017
概括
碳复合物与二氧化碳 (CO2) 和甲 (CH4) 具有选择性的反应性. 虽然一些复合物是无反应的,但[Re(CO) 2+会激活CO2,但随后的甲合是有限的.
科学领域:
- 有机金属化学
- 催化剂
- 计算化学
背景情况:
- 碳复合物正在研究它们在激活小分子方面的潜力.
- 了解金属复合物与二氧化碳和甲的反应性对于催化是至关重要的.
研究的目的:
- 通过碳复合物探索二氧化碳和甲的激活和合.
- 阐明反应机制并确定控制反应性的因素.
主要方法:
- 使用里埃变换离子环子共振质谱 (FT-ICR MS) 的气相实验.
- 在高层次的量子化学计算中.
主要成果:
- 复合物[Re(CO) 2+自发地从CO2中抽取一个氧原子.
- 标记实验表明新生成的CO配体的优先消除.
- [ORe(CO) 2+与CH4反应形成二甲基复合物,但CH2=C=O合不发生.
- 复合物与甲基联体 ([Re(CO) x(CH2) ]+) 对二氧化碳没有反应.
结论:
- 碳复合物对二氧化碳和CH4具有明显的反应模式.
- 观察到的反应性受复合物的结构和特定反应途径的影响.
- 量子化学计算提供了这些反应的机理细节.
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