研究室工作進展, 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.亮點介紹
金屬雜環戊二烯，作為一類重要的金屬有機雜五元環化合物，其合成、分離及反應，受到了許多金屬有機化學家的關注。盡管元素周期表中s區、p區及d區的金屬雜環戊二烯已有報道，但含稀土元素的金屬雜環戊二烯文獻還沒有報道。最近，我們從二锂試劑出發，合成了首例含稀土元素镥的雜環戊二烯。該镥雜環戊二烯能與多種小分子，如新戊醛、單質硒、二氧化碳、異腈等反應，合成了多種镥雜環化合物。該研究初步表明了镥雜環戊二烯中的兩個Lu–C(sp2)鍵的協同反應性。該文被歐洲化學雜志選為了Hot Paper, 并且在ChemistryViews作為亮點介紹(http://www.chemistryviews.org/details/ezine/7835431/Rare-Earth_Metallacycles.html)。