A wide spectrum of challenging organic and inorganic transformations can be facilitated by employing appropriate catalysts; such as ligated metals. Indeed, it is worth to mention that the performance of a ligated-metal catalyst can be influenced by various reaction conditions; these influential conditions include the nature of the ligand, ligation state of the metal, and contribution of the solvent. Difluoroalkylation of organic target molecules is very attention-grabbing reaction that has recently gained growing interest; e.g. the palladium-catalyzed difluoroalkylation of aldehyde-derived hydrazones. However, it is must be mentioned that there is still several unanswered questions and challenging tasks related to the corresponding proposed catalytic mechanisms. We report here in computational insights into a proposed mechanism that has been recently reported in the literature. Selected computational chemical methods were employed; this includes using hybrid density functional theory (DFT), ONIOM (DFT/MM), and NBO approaches. Various geometrical and molecular properties of selected reactants and the corresponding intermediates, transition states, and products were simulated; this includes bonds’ lengths and angles, the atomic charges based on the analysis of the natural bond orbital (NBO); thermodynamic quantities, frontier orbitals (HOMO and LUMO), dipole moment, and IR spectra. Notably, obtained geometrical results revealed significant difference for the effect of the terminal amino group, including bond angles and lengths, atoms related to the center of reactions. The thermodynamic quantities were calculated for all mechanistic steps and the corresponding energy diagrams was constructed. Interestingly, the energy diagram provides insightful image for each mechanism, and more conclusive information can be provided accordingly.

Computational mechanistic insights into the palladium-catalyzed alkylation of selected aldehyde-derived hydrazones

255th National Meeting (2018)

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