一个动因化物金属cyclopropene复合物:合成,结构,反应性,和计算研究
Bo Fang1, Wenshan Ren, Guohua Hou
1Department of Chemistry, Beijing Normal University , Beijing 100875, China.
Journal of the American Chemical Society
|December 3, 2014
概括
研究人员合成了第一个稳定的活性化物金属cyclopropene,一个二磁性 (IV) 复合体. 这种化合物与各种不和分子具有独特的反应性,与4组金属不同.
科学领域:
- 有机金属化学 有机金属化学
- 动因化物化学 动因化物化学
- 合成无机化学 合成无机化学
背景情况:
- 乙胺有机金属化合物对于理解基本的化学键和反应性至关重要.
- 金属cyclopropenes是有机合成的多功能中间体,但它们的动因类类似物是未经探索的.
- 复合体由于5f轨道的参与而具有独特的电子特性.
研究的目的:
- 合成和表征第一个稳定的活性化物金属cyclopropene.
- 研究合成复合物的结构,电子和结合性质.
- 为了探索actinide金属cyclopropene与各种不和基质的反应性,并与4组金属进行比较.
主要方法:
- 在乙烯存在的情况下通过减少前体与石墨的合成.
- 使用磁感应度测量进行结构性表征.
- 使用密度函数理论 (DFT) 进行计算分析,以了解电子结构和结合.
- 用和异质不和分子进行反应性研究.
主要成果:
- 首个稳定的活性化物金属cyclopropene, [η(5) -1,2,4-(Me3C) 3C5H2]2Th(η(2) -C2Ph2),已成功合成.
- 磁性易感性证实了该复合物是二磁性Th (IV) 物种.
- DFT的计算揭示了Th 5f轨道对金属cyclopropene结合的显著贡献.
- 该复合物与酸盐没有反应性,但与化物,酸盐,碳胺,亚酸盐,亚酸盐和酸盐反应.
- 与4组金属相比,表现出明显的反应模式.
结论:
- 一种稳定的活性化物金属cyclopropene的合成在活性化物有机金属化学开辟了新的途径.
- 电子结构和结合受5f轨道的参与影响.
- 金属cyclopropenes的独特的反应性概况表明在催化和合成的潜在应用.
- 与4组金属相比,的明显反应性突出显示了它在周期表中的独特地位.
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