第4组金属二 (二) 乙烯复合物的合成,表征和反应性 - - 一项反应性和结合性研究
Martin Haehnel1, Sven Hansen, Kathleen Schubert
1Leibniz-Institut für Katalyse e.V. an der Universität Rostock , Albert-Einstein-Str. 29a, D-18059 Rostock, Germany.
Journal of the American Chemical Society
|October 26, 2013
概括
这项研究探讨了二二) 乙烯与4组金属的协调,产生新的单核和双核复合物. 观察到一个紧张的四个成员的异金属循环,在有机金属化学中表现出独特的反应性和结合性.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
背景情况:
- 双基酸乙烯 (Ph2P-CC-PPh2) 是一种在协调化学中的多功能联体.
- 第4组金属 (和) 是催化和材料科学中的关键成分.
- 了解有机联体与金属联体的反应性和结合性对于开发新的合成方法至关重要.
研究的目的:
- 为了研究二二 (二二) 乙烯与4组金属的协调化学反应.
- 合成和描述新的单核和双核复合体.
- 探索压力异金属循环的形成及其反应性.
主要方法:
- 合成单核复合体Cp*2Ti(η(2) -Ph2PC2PPh2), (rac-ebthi) Ti(η(2) -Ph2PC2PPh2和 (rac-ebthi) Zr(η(2) -Ph2PC2PPh2).这些复合体的合成方法包括:
- 二核复合体[Cp2Zr(η(2) -Ph2PC2PPh2) ]2和应变异金属循环复合体7b.b的形成和分离.
- 复合物与其他金属中心的反应,包括Ni(0),导致C-P键裂变.
- 通过X射线结晶学和DFT分析进行表征.
主要成果:
- 成功合成了4组金属的单核和双核复合物与乙烯.
- 一个高度紧张的四个成员的异金属循环的隔离,这是一个罕见的循环单元,涉及氨酸片段.
- 对单核复合体和双核复合体在与其他金属碎片反应中的不同反应性的观察.
- 在与Ni(0) 复合体反应后,在复合体中证明了C-P键裂变.
结论:
- 双二酸乙烯与4组金属具有多种协调模式,从而形成独特的复杂结构.
- 压力异金属循环的形成凸显了这些系统的丰富反应性.
- 该研究提供了关于有机金属化学中有机联体的稳定性和反应性的见解.
- DFT分析支持拟议的结合模式和复杂结构,包括为化合物7b.提出的翻转式协调.
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