Free Radical Scavenging Activity and Inhibition of Enzyme-Catalyzed Oxidation by trans-aryl-Palladium Complexes

Herein, nine square planar <i>trans</i>-arylbis(triphenylphosphine)palladium halides (PdX(PPh₃)₂Ar) were synthesized and fully characterized. The molecular structure of two complexes (<b>1</b> and <b>2</b>) have been determined by both X-ray diffraction and described thanks to Hirshfeld surface analysis. Investigation of the antioxidant activities showed that most of the complexes exhibit a strong dose-dependent radical scavenging activity towards DPPH radical as well as in the ABTS radical scavenging test. Complexes <b>1</b> [PdI(PPh₃)₂(4-MeOC₆H₄)] and <b>3</b> [PdCl(PPh₃)₂(4-MeOC₆H₄)] showed the highest activity in the DPPH assay with EC₅₀ values of 1.14 ± 0.90 and 1.9 ± 0.87 µM, respectively. In contrast, for the ABTS assay, quercetin (5.56 ± 0.97 µM) was slightly more efficient than the three complexes <b>1</b> (5.78 ± 0.98 µM), <b>2</b> (7.01 ± 0.98 µM), and <b>3</b> (11.12 ± 0.94 µM). The use of kinetic studies as a powerful parameter shows that complexes <b>1</b>, <b>2</b>, and <b>3</b> displayed the best antioxidant efficiency. The antioxidant effect of the nine palladium complexes has been also evaluated on the enzyme-catalyzed oxidation of the L012 probe (using HRP/H₂O₂) by using a chemiluminescence technique. As with the last model, complexes <b>1</b>, <b>2</b>, and <b>3</b> showed the best activity, with EC50 values of 3.56 ± 1.87, 148 0.71, and 5.8 ± 2.60 µM, respectively. Interestingly, those complexes (<b>1</b>, <b>2</b>, and <b>3</b>) even exhibited a higher dose-dependent activity than the quercetin (7.06 ± 2.56 µM) used as a standard. Taken together, the combined results reveal that the antiradical and enzyme (HRP) inhibitory activity of complexes decrease following the ligand order of <i>p</i>-OMePh > <i>p</i>-OAcPh >> Ph.