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Updated: Oct 21, 2025

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
One-Step Synthesis and Schlenk-Type Equilibrium of Cyclopentadienylmagnesium Bromides
Philipp Schüler1, Helmar Görls1, Sven Krieck1
1Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldtstraße 8, 07743, Jena, Germany.
Abstract:
In the in situ Grignard metalation method (iGMM), the addition of bromoethane to a suspension of magnesium turnings and cyclopentadienes [C5 H6 (HCp), C5 H5 -Si(iPr)3 (HCpTIPS )] in diethyl ether smoothly yields heteroleptic [(Et2 O)Mg(CpR )(μ-Br)]2 (CpR =Cp (1), CpTIPS (2)). The Schlenk equilibrium of 2 in toluene leads to ligand exchange and formation of homoleptic [Mg(CpR )2 ] (3) and [(Et2 O)MgBr(μ-Br)]2 (4). Interfering solvation and aggregation as well as ligand redistribution equilibria hamper a quantitative elucidation of thermodynamic data for the Schlenk equilibrium of 2 in toluene. In ethereal solvents, mononuclear species [(Et2 O)2 Mg(CpTIPS )Br] (2'), [(Et2 O)n Mg(CpTIPS )2 ] (3'), and [(Et2 O)2 MgBr2 ] (4') coexist. Larger coordination numbers can be realized with cyclic ethers like tetrahydropyran allowing crystallization of [(thp)4 MgBr2 ] (5). The interpretation of the temperature-dependency of the Schlenk equilibrium constant in diethyl ether gives a reaction enthalpy ΔH and reaction entropy ΔS of -11.5 kJ mol-1 and 60 J mol-1 , respectively.
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