通过Fe-Hydrazido休息状态将N2转化为N ((SiMe3)
Adam D Piascik1, Ruohao Li1, Harry J Wilkinson1
1Department of Chemistry , Imperial College London , Exhibition Road , South Kensington, London SW7 2AZ , United Kingdom.
Journal of the American Chemical Society
|August 18, 2018
概括
铁催化剂有效地将气 (N2) 转化为化胺,实现创纪录的产量. 机理学研究揭示了一条涉及中间化,减少和不成比例的途径,随后是N-N键裂变.
科学领域:
- 一致性催化
- 有机金属化学
- 固定的方法
背景情况:
- 将N2转化为有价值的产品至关重要.
- 对N2激活的3d过渡金属催化剂的机制理解有限.
研究的目的:
- 研究铁复合物的催化机制以进行N2转化.
- 从N2中获得N3的高产量.
主要方法:
- 使用的铁复合物Fe (PP) 2 (N2) 具有PP=R2PCH2CH2PR2 (R=Me, Et).
- 使用石墨 (KC8) 和三甲化物 (Me3SiCl) 作为试剂.
- 结合密度函数理论 (DFT) 计算的实验研究.
主要成果:
- 在N3) 3从N2生产中获得了最高的铁基催化剂产量.
- 提出了一种涉及电友Nβ化和1e-还原以形成FeI(NN-SiMe3) 介质的机制.
- 鉴定了FeII[N-N(SiMe3) 2物种作为催化休息状态,随后是N-N键裂变.
结论:
- Fe (PP) 2 (N2) 复合物是N2转换的高度有效的催化剂.
- 拟议的机制为3D金属催化N2固定提供了关键的机械洞察力.
- 实验和计算数据支持阐明的催化循环.
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