了解从基基中产生分支基的化催化剂
Paul Dingwall1, José A Fuentes1, L. Ellis Crawford1
1School of Chemistry, University of St. Andrews, EaStCHEM, St. Andrews, Fife KY16 9ST, United Kingdom.
Journal of the American Chemical Society
|October 26, 2017
概括
这项研究揭示了独特的BOBPHOS连接物如何使催化水合形成,从简单的中选择性地产生分支化物,这是催化学的重大进步.
科学领域:
- 有机金属化学
- 催化剂
- 有机合成
背景情况:
- 水合成型是生产化物的一个关键工业过程.
- 从无偏的基中获得高分支化具有挑战性.
- 具有特殊连接体的催化剂对于控制选择性至关重要.
研究的目的:
- 阐明催化水合反应的机制.
- 了解使用BOBPHOS联体的高选择性产品的起源.
- 研究CH-π相互作用在指导选择性的作用.
主要方法:
- 实验研究包括动力分析,现场高压IR (HPIR),NMR光谱和标签研究.
- 使用能量跨度和TOF控制分析的计算调查.
- 开发一个3D象限模型来解释区域和enantioselectivity.
主要成果:
- 在催化循环中确定了两个决定营业额的步骤.
- 观察到CO的负顺序和和H2的部分压力的正顺序.
- 关键-和-中间体的光谱表征.
- 证实分支为线性乙烯基比率预测最终的化物产品比率.
- 发现了影响高分支选择性的稳定性CH-π相互作用.
结论:
- 在催化水合形成过程中,BOBPHOS连接体对于实现高分支选择性至关重要.
- 在指导反应途径方面,CH-π相互作用起着重要作用.
- 实验和计算数据提供了全面的机制理解.
- 开发的模型解释了区域和enantioselectivity的起源.
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