Synthesis and Structural Characterization of Butadienylcalcium-based Heavy Grignard Reagents and a Ca-4[O] Inverse Crown Ether Complex
Synthesis and Structural Characterization of Butadienylcalcium-based Heavy Grignard Reagents and a Ca-4[O] Inverse Crown Ether Complex
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丁二烯基钙基重格氏试剂和 Ca-4[O] 反冠醚配合物的合成及结构表征
DOI：
10.1002/anie.201704176
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发表时间：
2017
影响因子：
16.6
通讯作者：
Xi Zhenfeng
中科院分区：
文献类型：
--
作者：
Wei Baosheng;Liu Liang;Zhang Wen-Xiong;Xi Zhenfeng
重格利雅试剂（RAeX，Ae=Ca，Sr，Ba，X=卤化物）的结构解析一直受到人们的极大关注，主要是因为它们的难接近性和显著的不稳定性。以碘化钙和1，4-二硫代-1，3-丁二烯为原料，合成了一系列丁二烯钙化合物，包括1-钙-4-锂-1，3-丁二烯、1，4-二钙-1，3-丁二烯和Ca 4 [O]反冠醚配合物。这些前所未有的重质格氏试剂的单晶X射线分析揭示了独特的结构特征和键合模式。初步反应化学进行了研究。本研究提供了一类新的烯基重格利雅试剂和有用的合成策略，否则不可用的反应性有机金属化合物。
The structure elucidation of heavy Grignard reagents (RAeX, Ae=Ca, Sr, and Ba, X=halides) has been greatly strived after, mainly because of their inaccessibility and remarkable instability. The synthesis of a series of butadienylcalcium compounds is presented, including 1‐calcio‐4‐lithio‐1,3‐butadiene, 1,4‐dicalcio‐1,3‐butadiene, and a Ca4[O] inverse crown ether complex, via the reaction between 1,4‐dilithio‐1,3‐butadienes and calcium iodide in THF. Single‐crystal X‐ray analysis of these unprecedented heavy Grignard reagents revealed unique structural characteristics and bonding modes. Preliminary reaction chemistry was investigated. This study provides a novel class of alkenyl heavy Grignard reagents and a useful synthetic strategy for otherwise unavailable reactive organometallic compounds.