通过动态突变异构体的Si-H激活:一种由基导向的途径到脱联的脱联
Manuel Kümper1, Franz F Westermair2, Tobias Götz1
1Faculty of Chemistry and Pharmacy, Institute of Inorganic Chemistry, University of Regensburg, Universitätsstraße 31, D-93053, Regensburg, Germany.
Angewandte Chemie (International ed. in English)
|September 30, 2025
概括
锡兰与锡兰醇的无金属脱配合依赖于中间体的动态异构. 连接物设计控制化物位置,使选择性Si-O键形成和通过Berry伪旋转释放.
科学领域:
- 有机化学 有机化学
- 可持续化学 可持续化学
背景情况:
- 脱配合 (DHC) 为Si-O键形成提供了一种可持续的方法.
- 在没有金属的DHC中释放的机制 二和二的释放机制尚不清楚.
研究的目的:
- 为了阐明在无金属DHC反应中释放的机制.
- 调查中间体异构在Si-H激活和H2演化中的作用.
主要方法:
- 使用了经过硬化定制的钻石化.
- 采用了多核可变温度NMR光谱学.
- 执行了量子化学计算.
主要成果:
- 确定了五坐标中间体的动态顺序异构,对于Si-H激活和H2释放至关重要.
- 证明了使轴性化物配置成为可能的配体促进了Si-O合和H2消除.
- 表明N-tert-butyl替代阻碍H2释放通过稳定赤道化物配置,导致Si-N键裂变.
- 揭示了赤道和轴向化物配置之间的平衡,促进了贝里伪旋转和进化.
结论:
- 五坐标中间体的动态同质性对于无金属Si-H激活和H2释放至关重要.
- 连接体设计可以指导中间体异构,使选择性Si-O键形成和受控的H2进化.
- 作为设计选择性,无金属的Si-H激活过程的原则,建立了连接体导向的异构体.
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