非化d0氧化-烯复合物
Edward J Stoebenau1, Richard F Jordan
1Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637, USA.
Journal of the American Chemical Society
|June 22, 2006
概括
本研究详细介绍了无基复合物的合成和基协调. 由于缺乏d-pi*背接,该复合体表现出不对称的基因结合,影响了协调强度.
科学领域:
- 有机金属化学 有机金属化学
- 酸催化剂的催化方法
- 奥莱芬协调化学 奥莱芬协调化学
背景情况:
- conocene复合物是olefin聚合中的重要催化剂.
- 了解连接体结合和电子效应对于催化剂设计至关重要.
- 没有基的金属化合物具有独特的反应性.
研究的目的:
- 为了合成和表征一种新的无基氧复合物.
- 为了研究各种基因与这个复合物的协调行为.
- 阐明控制烯结合的电子和固态因素.
主要方法:
- 使用Cp'2Zr(O(t) Bu) Me和三乙酸盐合成一种无基的conocene复合物.
- 核磁共振光谱 (1H,13C,19F) 用于研究复合物形成和基协调.
- 可变温度NMR分析动态过程并确定平衡常数.
主要成果:
- 一个没有基的复合物,[Cp'2Zr(O(t) Bu)][B(C6F5) [4],已成功合成.
- 核磁共振数据显示了非对称的烯结合和C=C结合的极化.
- 对基协调的平衡常数显示出基于基结构的显著变化,其中基基表现出最强的结合.
结论:
- 在复合体中缺乏d-pi*背接,导致独特的极化和结合.
- 立体和电子因素强烈影响烯协调亲和力.
- 观察到的动态过程为这些有机金属复合物的流动行为提供了洞察力.
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