Mechanochemistry is an emerging field with many potential applications in sustainable chemistry. But despite the growing interest on the field, its underlying mechanistic foundations are not fully understood yet. This work presents the application of computational tools, such as DFT calculations in continuum and microkinetic modeling, to the analysis of mechanically activated procedures. Two reactions reported in previous experimental publications are studied: 1) a series of Diels‐Alder reactions and 2) the synthesis of sulfonylguanidines. Calculations succeed in reproducing experimentally reported reaction times. The procedures are mostly standard, coupled with some sensitive choices in terms of starting concentrations and dielectric constant. This means that these particular reactions accelerated by ball milling follow the same mechanism as the equivalent reactions in solution. The implications of this result on the general picture of mechanochemical processes are discussed.
Understanding ball milling mechanochemical processes with DFT calculations and microkinetic modeling
ChemSusChem. 2021, 14 (13), 2763-2768, DOI: 10.1002/cssc.202100497.