Simulating the Chelate Effect.

Despite the rich history of experimental studies focusing on the thermochemistry and kinetics associated with the chelate effect, molecular-level computational studies on the chelate ring opening/ring closure are scarce. The challenge lies in an accurate description of both the metal ion and its aqueous environment. Herein, we demonstrate that an optimized 12-6-4 Lennard-Jones (LJ) model can capture the thermodynamics and provide detailed structural and mechanistic insights into the formation of ethylenediamine (en) complexes with metal ions. The water molecules in the first solvation shell of the metal ion are found to facilitate the chelate ring formation. The optimized parameters further simulate the formation of bis and tris(en) complexes representing the wide applicability of the model to simulate coordination chemistry and self-assembly processes.