在胺稀土复合物中的前所未有的反应模式:一项联合实验理论研究
Haiwen Tian1, Jianquan Hong1, Kai Wang1
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University , Shanghai 200433, People's Republic of China.
Journal of the American Chemical Society
|December 23, 2017
概括
三核稀土金属复合物与各种小分子反应,形成新的化合物. 一个与二硫化碳的独特反应揭示了一个不寻常的双重脱硫/合/循环路径.
科学领域:
- 有机金属化学
- 稀土金属复合物
- 化学
背景情况:
- 已知三核稀土金属复合物具有功能化的胺联体.
- 这些复杂物与小分子的反应性是正在进行的研究领域.
研究的目的:
- 研究三核稀土金属复合物与各种小分子的反应.
- 阐明反应机制并确定所产生的含产品.
- 探索二硫化碳与这些复合物的异常反应性.
主要方法:
- 三核稀土金属复合物的合成 [L3Ln3 ((μ2-Me) 2 ((μ3-Me) 3 ((μ3-η1:η2:η2-PC6H4-o)) ] (Ln = Y, Lu).
- 与乙烯,二氧化碳,二甲,异化物,PhSSPh和CS2发生反应.
- 使用分析技术对产品进行表征.
- 密度函数理论 (DFT) 计算以确定反应途径.
主要成果:
- 通过与各种小分子的反应形成一系列含产物.
- 从与CS2的反应中分离出两种新型P-甲基-二酸复合物.
- 对CS2异常的脱硫/合/循环反应模式的观察.
- DFT的计算支持了提出的反应途径,突出显示了素联体的降解功率.
结论:
- 三核稀土金属胺复合物与小分子具有多种反应性.
- 碳二硫化物经历了一种独特的双重反应路径,包括脱硫,合和循环.
- 在CS2反应中,胺配体的降解能力对于C-S键裂变至关重要.
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