一氧化碳的选择性同型和异型合
Yuwen Wang1, Arseni Kostenko1, Terrance J Hadlington1
1Metalorganics and Inorganic Materials, Department of Chemistry , Technische Universität Berlin , Straße des 17. Juni 135, Sekr. C2 , 10623 Berlin , Germany.
Journal of the American Chemical Society
|December 6, 2018
概括
双价可以选择性地将一氧化碳 (CO) 合并为二氧化. 这项研究揭示了一种新的机制,即以路易斯酸的形式激活了二氧化碳,与过渡金属不同.
科学领域:
- 有机化学
- 无机化学
- 催化剂
背景情况:
- 过渡金属主导一氧化碳 (CO) 转化为多碳化合物.
- 通过介导的二氧化碳分裂和脱氧降解合是罕见的,而且人们对其了解甚少.
- 强大的CO键需要有效的激活策略.
研究的目的:
- 报告使用双价试剂的选择性去氧化同.
- 为了阐明二氧化碳激活和分裂的机制.
- 探索复合物与二氧化碳和异化物的反应性.
主要方法:
- 合成和表征双价复合物[LSi:) 2Xant 1a和 (LSi:) 2Fc 1b].
- 在温和条件下与一氧化碳反应复合物.
- 密度函数理论 (DFT) 计算以调查反应机制.
- 与异化物 (Xyl-NC) 进行反应,以探测CO激活途径.
主要成果:
- 通过二价复合物1a和1b对CO进行选择性脱氧同,以形成二基.
- 证明了Si·Si距离在CO结合和激活中的关键作用,与无反应的模拟物1c.
- DFT计算显示CO在介导激活中充当路易斯酸 (四电子受体),与过渡金属催化形成鲜明对比.
- 通过与Xyl-NC的反应形成的独特的化和二化产物.
- 首次实现了二氧化碳与异化物的选择性异对接.
结论:
- 在温和的条件下,双价试剂可以选择性地同一氧化碳.
- 该机制涉及CO作为易斯酸,这是CO激活的新途径.
- 具有独特的电子特性, 能够激活小分子的新反应模式.
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