Mechanochemistry Unveiled: Non-Covalent Interactions, Cocrystals, and Polymorphism in Cyclorhodation Reactions

Abstract

ABSTRACT: Systematic investigations into the mechanochemical metal-catalyzed functionalization of C–H bonds have showcased its efficacy in chemical synthesis, surpassing traditional solution-based protocols.[1] Despite this progress, the mechanistic details underlying C–H bond activation in mechanochemical conditions remain poorly understood. This presentation delves into the mechanochemical synthesis of rhodacycles via ball milling of N-substrates and [Cp*RhCl2]2 in the presence of NaOAc. Notably, our study unveils through ex-situ and in-situ instrumental analyses the formation and polymorphic transformation of cocrystal intermediates between substrates and the rhodium dimer preceding the C–H activation step.[2] Furthermore, computational investigations have elucidated the stability and reactivity of these cocrystals towards acetate ion-mediated reactions. [3-4] By shedding light on these mechanistic nuances, our research advances the understanding and potential applications of mechanochemical C–H activation processes. REFERENCES

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[2] K. J. Ardila-Fierro, M. Rubčić, J. G. Hernández, Chem. Eur. J. 2022, 28, e202200737

[3] J. G. Hernández, K. J. Ardila-Fierro, S. Gómez, T. Stolar, M. Rubčić, E. Topić, C. Z. Hadad, A. Restrepo, Chem. Eur. J. 2023, 29, e202301290

[4] S. Gómez, S. Gómez, N. Rojas-Valencia, J. G. Hernández, K. J. Ardila-Fierro, T. Gómez, C. Cárdenas, C. Hadad, C. Capelli, A. Restrepo. Phys. Chem. Chem. Phys. 2024, 26, 2228.