Premium
Structure and Reaction Chemistry of Magnesium Organocuprates Derived from Magnesiacyclopentadienes and Copper(I) Salts
Author(s) -
Liu Liang,
Wei Junnian,
Chi Yue,
Zhang WenXiong,
Xi Zhenfeng
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607355
Subject(s) - transmetalation , chemistry , magnesium , reactivity (psychology) , magnesium bromide , bromide , organic chemistry , polymer chemistry , combinatorial chemistry , inorganic chemistry , catalysis , medicine , alternative medicine , pathology
The chemistry of magnesium organocuprates, including their synthesis, structures, and reactions, remains underexplored. In this work, by taking advantage of the high reactivity and ready availability of magnesiacyclopentadienes, a series of magnesiacyclopentadiene‐based organocuprates were synthesized and structurally characterized. A variety of CuX salts (X=Cl, Br, I, or alkynyl) were successfully applied to react with magnesiacyclopentadienes. Besides CuX salts, AgX salts (X=Cl, alkynyl) also undergwent the above reaction to afford the corresponding magnesium organoargentates. Single‐crystal X‐ray structural analysis and DFT calculations of these butadienyl magnesium organocuprates revealed unique structural characteristics and bonding modes. These results are also very useful to understand the transmetalation process, since the product can be viewed as the resting‐state intermediate of a transmetalation reaction between organomagnesium compounds and coinage‐metal salts. Preliminary information on the reaction chemistry of these magnesium organocuprates is provided by their reactions with allyl bromide, benzoyl chloride, and CO 2 .