Rare-Earth Metallacycloheptatrienes: Synthesis, Structure, and Reactivity

被引：4

作者：

Chai, Zhengqi ^{[1
,2
]}

Wei, Junnian ^{[1
,2
]}

Zhang, Wen-Xiong ^{[1
,2
]}

机构：

[1] Peking Univ, Coll Chem & Mol Engn, Beijing Natl Lab Mol Sci BNLMS, State Key Lab Rare Earth Mat Chem & Applicat, Beijing 100871, Peoples R China

[2] Peking Univ, Coll Chem & Mol Engn, Key Lab Bioorgan Chem & Mol Engn, Minist Educ, Beijing 100871, Peoples R China

来源：

ORGANOMETALLICS | 2023年 / 42卷 / 19期

基金：

国家重点研发计划;

关键词：

REDUCTIVE ELIMINATION; COMPLEXES; ALKYNES; ZIRCONACYCLOPENTADIENES; LUTETACYCLOPENTADIENE; DERIVATIVES; MECHANISM; SCANDIUM; CRYSTAL; ANALOGS;

D O I：

10.1021/acs.organomet.3c00301

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

As the key intermediates in metal-catalyzed [2 + 2 + 2] cycloaddition reactions of three alkynes, main-group and transitionmetal metallacycloheptatrienes have been studied for decades, but rareearth analogues have remained illusive. Herein, we report the well defined rare-earth metallacycloheptatrienes 2-Sc and 2-Lu obtained in high yields via the reaction of Cp*Li (Cp* = pentamethylcyclopentadienyl) and RECl3 (RE = Sc, Lu) with TMEDA-coordinated 2,2'dilithio-Z-stilbene 1. The single-crystal structure of 2-Sc (RE = Sc) reveals it to be a separate ion pair, and the scandacycloheptatriene ring adopts a nonplanar boat-like conformation. The reactivity of compounds 2-Sc and 2-Lu has been investigated. When 2-Sc was treated with 2,6-dimethylphenyl isocyanide, compound 3 was obtained via the successive 1,1-insertion and 1,2-insertion of the isocyanide. The structure of 3 was also fully characterized.

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页码：2736 / 2741

页数：6

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