切莱特受控合成的血清性安萨-齐尔科诺烯
Matthew D Lococo1, Xingwang Zhang, Richard F Jordan
1Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637, USA.
这项研究表明,胺复合物由于胺环中的扭曲形状而首选形成racemic ansa-metallocenes,从而影响合成过程中的立体化学.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 催化剂是一种催化剂.
背景情况:
- 合金复合物与酸连接体是金属合成中的关键前体.
- 金属形成的立体化学结果对于催化应用至关重要.
- 了解复合体中的形状偏好对于控制产品选择性至关重要.
研究的目的:
- 用一种特定的胺前体来研究安萨-金属的合成.
- 阐明胺酸联体的结构性行为及其对立体选择性的影响.
- 确定控制种族性比中等同体的优先形成的因素.
主要方法:
- 合成胺酸复合物及其与安萨-比斯-烯试剂的反应.
- 使用核磁共振 (NMR) 光谱学对产品的表征.
- 通过X射线晶体学确定分子结构.
主要成果:
- 在没有可检测的半同位素的情况下,获得了高产的种族性ansa-metallocenes (rac- ((XBI) Zr [PhN ((CH ((2)) ((3) NPh)).
- X射线晶体学揭示了Zr[PhN(CH(2))(3) NPh]环中的扭曲形状,将N-Ph群远离N-Zr-N平面.
- 这种观察到的形状补充了种族金属的结构,并破坏了 meso isomers 的稳定性.
结论:
- 建议Zr[PhN(CH(2)) ((3) NPh]环的扭曲形状在添加第二个内基联体时指导立体化学.
- 过渡状态中的这种形状偏好导致了强烈的偏见,即种族产品的形成.
- 这些发现提供了对金属合成中的立体控制的见解,并得到了其他胺前体的研究的支持.
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