Indacyclopentadienes and Aromatic Indacyclopentadienyl Dianions: Synthesis and Characterization
Indacyclopentadienes and Aromatic Indacyclopentadienyl Dianions: Synthesis and Characterization
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茚达环戊二烯和芳香族茚达环戊二烯基双阴离子：合成和表征
DOI：
10.1002/chem.201806356
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Xi Zhenfeng
中科院分区：
文献类型：
--
作者：
Zhang Yongliang;Yang Zhenqiang;Zhang Wen Xiong;Xi Zhenfeng
首次合成了一系列未见文献报道的金属杂环化合物，包括茚并环戊二烯（2）、螺环茚并环戊二烯（3）、含In-Li键的芳香茚并环戊二烯二价阴离子（4）和含In-In键的芳香茚并环戊二烯二价阴离子（5），并通过单晶X射线结构分析对其进行了结构表征。通过1，4-二硫代-1，3-丁二烯与InCl 3反应合成了茚并环戊二烯2和3。观察到2和3之间的结构转变。用过量的锂还原茚并环戊二烯2，根据环上取代基的不同，分别得到含In-Li键的芳香族茚并环戊二烯二阴离子4和含In-In键的芳香族茚并环戊二烯二阴离子5。实验测定和理论分析均证实了4和5的芳香性。
A series of unprecedented metallacycles of indium, including indacyclopentadienes (2), spiro indacyclopentadienes (3), aromatic indacyclopentadienyl dianions with an In−Li bond (4), and aromatic indacyclopentadienyl dianions with an In−In bond (5), were synthesized and structurally characterized by single‐crystal X‐ray structural analysis for the first time. Both indacyclopentadienes2and3were synthesized by reaction of 1,4‐dilithio‐1,3‐butadienes with InCl3. Structural transformations between2and3were observed. Reduction of indacyclopentadienes2with an excess amount of lithium afforded aromatic indacyclopentadienyl dianions4with an In−Li bond or5with an In−In bond, respectively, depending on the substituents on the ring. The aromatic character of4and5was confirmed by both experimental measurements and theoretical analysis.