Synthesis and Structural Characterization of Butadienylcalcium‐based Heavy Grignard Reagents and a Ca4[O] Inverse Crown Ether Complex

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‐butadie...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2017-07, Vol.56 (31), p.9188-9192
Main Authors: Wei, Baosheng, Liu, Liang, Zhang, Wen‐Xiong, Xi, Zhenfeng
Format: Article
Language:English
Subjects:
1,3-Butadiene
Barium
Butadiene
butadienylcalcium compounds
Calcium
Chemical bonds
Crystal structure
Halides
heavy Grignard reagents
inverse crown ether
Iodides
organocalcium compounds
Organometallic compounds
Reagents
Single crystals
Stability
Strontium
Structural analysis
Synthesis
X ray analysis
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Summary: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. Ca makes it: A series of butadienylcalcium compounds were synthesized by transmetalation of 1,4‐dilithio‐1,3‐butadienes with calcium iodide in THF. Single‐crystal X‐ray analysis of these heavy Grignard reagents revealed their unique structural characteristics and bonding modes. A Ca4[O] inverse crown ether complex was also discovered.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201704176