To probe the tendency of MgCl2 to break down the LiCl cluster, we ran AIMD at a 1:1 LiCl:MgCl2 concentration, reporting a dramatic effect of MgCl2 on the compactness of LiCl. Upon binding, the newly formed bimetallic moiety undergoes rapid structural evolution, deforming the originally tight Li4Cl4 unit. Relaxation of the cluster occurs through sequential cleavages of Li-Cl bonds, and consequent opening of Li(µ-Cl)2Li rings (Figure ). The LiCl moiety evolves along structures that closely recall the ones detected along the pathway of formation of Li4Cl4 (Figures ), transitioning into an open cubane moiety resembling R5, a ladder conformation (B6), and a condensed [4:2:0] bicyclic entity (R7). In these structures, MgCl2 remains outside the decomposing Li4Cl4 cluster, connecting as Mg(µ-Cl)2Li fourmember rings (Figure ). Within 10 ps, the LiCl cluster reaches a structure comprising a single LiCl unit held on either side by homonuclear Li(µ-Cl)2Li and mixed Mg(µ-Cl)2Li rings (Figure ). Such rapid evolution testifies how the electron-withdrawing power of MgCl2 is sufficient to destroy the cohesive interactions within Li4Cl4. Moreover, the occurrence of a central, linear LiCl unit, stabilized on both sides by small polynuclear Li:Mg:Cl aggregates suggests several scenarios. Firstly, this exposed LiCl unit is more likely to participate in forthcoming reactions. Also, heterolytic cleavage of the central Li-Cl bond may be facilitated by the stabilizing effect of the terminal aggregates. Such event could yield reactive ionic entities with active Li + and Cl -centers, 30 despite a low dielectric solvent that would, per se, disfavor ionic separation. AIMD employed a 1:1 LiCl:MgCl2 stoichiometry, while experiments typically use a 1:1 LiCl:RMgX ratio. Thus, the resulting LiCl:MgCl2 ratio should not exceed 2:1, assuming a quantitative shift of the Schlenk equilibrium induced by favorable LiCl-MgCl2 binding. Our computations were set up to favor conformational sampling in an affordable time for AIMD. Despite the excess concentration, the structures observed in simulations involved the direct interaction of Li4Cl4 with only two MgCl2 molecules, while other MgCl2 engaged peripherally through the dandling Mg-Cl bonds (Figure ). Thus, the reported events are compatible with the experimentally more relevant 2:1 LiCl:MgCl2 ratio. This study moves a critical step further into the comprehension of the chemistry of LiCl in ethereal solution, and its interaction with Grignard species. LiCl emerges as a highly dynamic system, whose selective affinity for MgCl2 deeply modifies the Schlenk equilibrium of Grignard reagents, in favor of MgR2. Interaction with excess MgCl2 evolves the LiCl cluster toward a solubilization pathway otherwise energetically unfavorable. Solubilization involves transient structures related to those detected in crystalline samples. This confirms the existence of several energetically similar conformations for solvated LiCl, which may be stabilized by marginal changes in the environmental conditions. Disintegration of Li4Cl4 by MgCl2 yields exposed LiCl moieties stabilized by small Li:Mg:Cl aggregates. Past experimental literature reported the presence of putative ionic species in turbo Grignard solutions. While a low dielectric medium would disfavor the presence of charged compounds, the existence of non-bridging LiCl stabilized by the Li:Mg:Cl aggregates opens the possibility of forming Li +and Cl --based ionic compounds. These charged moieties could interact with the organomagnesium compounds present in solution, yielding other species, of diverse reactivity. The LiCl-assisted enrichment of dialkylmagnesium confirms the original proposal by Knochel about its presence in solution, 2 and it is also in line with its recent characterization as tBu2MgClLi(THF)4 in the solid state. This work urges further investigation on the fragmentation of Li:Mg:X clusters into neutral and ionic compounds as a function of R, halides, and solvent, and on the consequences for turbo Grignard reagents.