New bis[MoO₂] and [MoO(O₂)] compounds: An artificial enzyme with peroxidase activity against o-phenylenediamine and...

In this study, two binuclear dioxido- and oxidoperoxido molybdenum (VI) complexes, [{Mo^VIO₂}₂(L)(H₂O)₂] 1 and [{Mo^VIO(O₂)}₂(L)(H₂O)₂] 2, were synthesized. Complex 1 was obtained through a 1:2 reaction of ligand I with MoO₂(acac)₂, while complex 2 was synthesized in situ by reacting MoO₃ with H₂O₂ in a 1:2 ratio. The structures and characteristics of the complexes were examined employing several techniques such as elemental (CHN) analysis, spectroscopy (FT-IR, UV-Vis, ¹H, and ¹³CNMR), and thermal study (TGA). SC-XRD analysis of complex 1a revealed that the molybdenum central atom adopts an octahedral geometry and is bonded to phenolic oxygen, enolate oxygen, and azomethine nitrogen atoms. Powder X-ray diffraction was used to determine the purity of the bulk material, and the results were compared to single crystal data. Computational calculations were performed using density functional theory (DFT) at the B3LYP/6-31G(d, p) level of theory for the ligand and the LANL2DZ level of theory for the complexes, yielding geometry optimized structures that were then employed in frequency and NMR-calculations. These theoretical findings were compared to the experimental results and showed a good correlation. Furthermore, the complexes exhibited peroxidase-like activity in the presence of hydrogen peroxide as evidenced by the oxidation of o-phenylenediamine and dopamine.