卡宾
碳负离子
化学
电泳剂
过渡金属卡宾配合物
配体(生物化学)
亲核细胞
药物化学
光化学
立体化学
有机化学
催化作用
生物化学
受体
作者
Zeming Huang,Ruru Wang,Tian Sheng,Xiangyang Zhong,Shaowu Wang,Xiancui Zhu,Qingbing Yuan,Yun Wei,Shuangliu Zhou
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2021-11-30
卷期号:60 (24): 18843-18853
被引量:5
标识
DOI:10.1021/acs.inorgchem.1c02589
摘要
The development of Fischer-type electrophilic carbene chemistry with early transition metals has been a great challenge due to the fact that such metals in their high oxidation states lack the d electrons to stabilize the electrophilic carbene. Herein, we disclose the first experimental and theoretical findings of in situ transformation of an sp2 carbanion to a Fischer-type electrophilic carbene with rare-earth metals in their high oxidation state with a d0 electron via electron transfer. The carbene may undergo 1,1-migratory insertion into an adjacent RE-C(sp3) bond, and an unprecedented ring opening of the indole ring of the ligand occurs when the carbenes undergo nucleophilic substitution with a special organolithium reagent o-Me2NC6H4CH2Li. The key to success is the uniquely tailored novel ligand systems featuring a suitable conjugate building block (-C═C-C═N) bearing an sp2 carbanion connected to the rare-earth metal center.
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