Morphological Plasticity of LiCl Clusters Interacting with Grignard Reagent in Tetrahydrofuran

[Image: see text] Ab initio molecular dynamics simulations are used to explore tetrahydrofuran (THF) solutions containing pure LiCl and LiCl with CH(3)MgCl, as model constituents of the turbo Grignard reagent. LiCl aggregates as Li(4)Cl(4), which preferentially assumes compact cubane-like conformations. In particular, an open-edge pseudotetrahedral frame is promoted by solvent-assisted Li–Cl bond cleavage. Among the Grignard species involved in the Schlenk equilibrium, LiCl prefers to coordinate MgCl(2) through μ(2)-Cl bridges. Using a 1:1 Li:Mg ratio, the plastic tetranuclear LiCl cluster decomposes to a highly solvated mixed LiCl·MgCl(2) aggregate with prevalent Li–(μ(2)-Cl)(2)–Mg rings and linear LiCl entities. The MgCl(2)-assisted disaggregation of Li(4)Cl(4) occurs through transient structures analogous to those detected for pure LiCl in THF, also corresponding to moieties observed in the solid state. This study identifies a synergistic role of LiCl for the determination of the compounds present in turbo Grignard solutions. LiCl shifts the Schlenk equilibrium promoting a higher concentration of dialkylmagnesium, while decomposing into smaller, more soluble, mixed Li:Mg:Cl clusters.