蒸的斯坦尼与10组d10过渡金属的协调化学:西拉斯坦尼与斯坦尼复合
Henning Arp1, Christoph Marschner, Judith Baumgartner
1Institut für Anorganische Chemie, Technische Universität Graz, Stremayrgasse 9, 8010 Graz, Austria.
Journal of the American Chemical Society
|May 1, 2013
概括
研究人员研究了蒸的斯坦尼与10组金属的协调方式. 产品的形成取决于金属,形成斯坦尼复合物,/形成锡拉斯坦复合物,受到硬质和电子因素的影响.
科学领域:
- 有机金属化学 有机金属化学
- 主群 化学 化学
- 计算化学计算化学
背景情况:
- 脱的斯坦尼是有机金属化学中的多功能联体.
- 了解它们与过渡金属的协调行为对于催化剂设计至关重要.
- 零价金属10组 (Ni,Pd,Pt) 提供多样化的电子和硬质环境.
研究的目的:
- 为了研究与Ni{0},Pd{0}和Pt{0}复合物的脱离型斯坦尼的协调化学.
- 阐明控制斯坦尼与西拉斯坦复合物的形成的因素.
- 在金属协调上探索连接物重新排列的机械路径.
主要方法:
- 脱的斯坦尼烯的PEt3添加物的合成和特征.
- 这些添加物与零价10组过渡金属前体的反应.
- 计算建模 (DFT) 用于研究反应机制和能量学.
- 分析影响产品分销的静电和电子效应.
主要成果:
- 优先形成金属斯坦尼烯复合体.
- 和主要产生了不寻常的西拉斯坦复合物.
- 计算研究揭示了最初的金属斯坦尼烯复合体形成,随后进行了重新排列.
- 异构化是一个具有小屏障的两步过程,表明热力学控制.
- 立体和电子因素决定了斯坦尼与西拉斯坦同体的相对稳定性.
结论:
- 脱的斯坦尼的协调行为高度依赖于10组金属.
- 固态和电子效应的微妙相互作用决定了观察到的产品选择性.
- 从斯坦尼到西拉斯坦的重新排列是一个由热力学驱动的协调后事件.
- 循环的disiylstannylenes喜欢Pd/Pt的silastannene复合物,而非循环的则喜欢Ni. stannylene复合物.
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