Unveiling the Catalytic Power of Molybdenum Complexes Formed from Acyl‐Hydrazones: Deciphering the Relationship Between Structure, Activity and Mechanisms

Molybdenum complexes featuring acyl‐hydrazones ligands with several substitutions, H 2 L, have been synthesized using classic solution‐based, hydrothermal, and mechanochemical techniques in diverse solvent environments. Elemental analysis (EA), infrared attenuated total reflection spectroscopy (IR‐ATR), and thermal gravimetric analysis (TGA) helped to elucidate the structural and thermal properties of these complexes. Single‐crystal X‐ray diffraction (SCXRD) experiments were conducted to determine the crystal and molecular structures of one ligand and six mononuclear complexes, denoted [MoO 2 (L)(D)] (D=MeOH, EtOH, H 2 O). The catalytic potential of those Mo compounds was explored in the (ep)oxidation reactions of cyclooctene as model substrate and linalool as natural substrate issued from biomass, employing aqueous tert ‐butyl hydroperoxide (TBHP) as an oxidising agent and no additional organic solvent. Experimental findings were complemented by theoretical density functional theory (DFT) calculations, establishing a correlation between experimental results and theoretical predictions. Insights gained from this comprehensive investigation shed light on the role of ligands in catalytic pathways for both cyclooctene and linalool oxidation, thereby advancing our better understanding of molybdenum‐based catalytic systems.