研究室工作进展, Apr. 24th, 2015
The First Lutetacyclopentadienes: Synthesis, Structure and Diversified Insertion/C−H Activation Reactivity
Ling Xu, Yu-Chen Wang, Junnian Wei, Yang Wang, Zitao Wang, Wen-Xiong Zhang,* and Zhenfeng Xi
Chem. Eur. J. 2015, 21, 6686-6689 (Hot paper and Highlighted by ChemistryViews).
Metallacyclopentadienes of s-, p- and d-block metals have received considerable attention in organic synthesis and organometallic chemistry over the past six decades because of their unique metallacyclic structure. In contrast, investigation on f-block metallacyclopentadienes is scarce. We report the first well-defined f-block lutetacyclopentadienes which are synthesised from pentamethylcyclopentadienyl lithium (Cp*Li), 1,4-dilithio-1,3-butadienes and LuCl3. The lutetacyclopentadiene shows excellent reactivity towards some small molecules, such as pivalaldehyde, Se, carbon dioxide and isonitrile to efficiently construct 3, 5, 7, 8 and 9-membered rare-earth metallacycles. The distinguished reactivity can be attributed to the highly ionic character and the cooperative reactivity of two Lu–C(sp2) bonds.亮点介绍
金属杂环戊二烯，作为一类重要的金属有机杂五元环化合物，其合成、分离及反应，受到了许多金属有机化学家的关注。尽管元素周期表中s区、p区及d区的金属杂环戊二烯已有报道，但含稀土元素的金属杂环戊二烯文献还没有报道。最近，我们从二锂试剂出发，合成了首例含稀土元素镥的杂环戊二烯。该镥杂环戊二烯能与多种小分子，如新戊醛、单质硒、二氧化碳、异腈等反应，合成了多种镥杂环化合物。该研究初步表明了镥杂环戊二烯中的两个Lu–C(sp2)键的协同反应性。该文被欧洲化学杂志选为了Hot Paper, 并且在ChemistryViews作为亮点介绍(http://www.chemistryviews.org/details/ezine/7835431/Rare-Earth_Metallacycles.html)。