title: Structure and Reaction Chemistry of Magnesium Organocuprates Derived from Magnesiacyclopentadienes and Copper(I) Salts.
abstract: 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 CO2.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, China.
authors.forename: Liang
authors.initials: L
authors.lastname: Liu
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, China.
authors.forename: Junnian
authors.initials: J
authors.lastname: Wei
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, China.
authors.forename: Yue
authors.initials: Y
authors.lastname: Chi
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, China.
authors.forename: Wen-Xiong
authors.initials: WX
authors.lastname: Zhang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, China.|State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai, 200032, China.
authors.forename: Zhenfeng
authors.initials: Z
authors.lastname: Xi
keywords: Cu−X bond cleavage; magnesiacyclopentadienes; magnesium organocuprates; organometallic compounds; transmetalation