Dinuclear Oxidovanadium(IV) and Dioxidovanadium(V) Complexes of 5,5′-Methylenebis(dibasic tridentate) Ligands: Synthesis, Spectral Characterisation, Reactivity, and Catalytic and Antiamoebic Activities

The synthesis of dinuclear oxidovanadium(IV) and dioxidovanadium(V) complexes of two hydrazones [CH2(H2sal‐nah)2 (I) and CH2(H2sal‐inh)2 (II)] derived from 5,5′‐methylenebis(salicylaldehyde) [CH2(Hsal)2] and nicotinic acid hydrazide (nah) or isonicotinic acid hydrazide (inh) is described. The compounds were characterised in the solid state and in solution, namely by spectroscopic techniques (IR, UV/Vis, EPR, 1H, 13C and 51V NMR). It has been demonstrated that the dioxidovanadium(V) complexes K2[CH2{VVO2(sal‐nah)}2]·2H2O (3), Cs2[CH2{VVO2(sal‐nah)}2]·2H2O (4) and Cs2[CH2{VVO2(sal‐inh)}2]·2H2O (5) of I and II are active in the oxidative bromination of salicylaldehyde by H2O2, therefore acting as functional models of vanadium‐dependenthaloperoxidases, and it has also been shown that the corresponding oxidovanadium(IV) complexes [CH2{VIVO(sal‐nah)(H2O)}2] (1) and [CH2{VIVO(sal‐inh)(H2O)}2] (2) are catalyst precursors for the catalytic oxidation, by peroxide, of methyl phenyl sulfide and diphenyl sulfide, yielding the corresponding sulfoxide and sulfone. Plausible intermediates involved in these catalytic processes are established by UV/Vis, EPR and 51V NMR studies. The dioxidovanadium(V) complexes along with ligands I and II were also screened against HM1:1MSS strains of Entamoeba histolytica. The results showed that the IC50 values of compounds 3 and 5 are lower than the IC50 value of metronidazole. The toxicity studies against human cervical (HeLa) cell lines showed that compounds 3 and 5 are not much toxic but are more toxic than metronidazole. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) Dinuclear VIVO (1 and 2) and VVO2 (3, 4 and 5) complexes of CH2(H2sal‐nah)2 (I) and CH2(H2sal‐inh)2 (II) have been synthesised, and their catalytic activities have been studied. Dioxidovanadium(V) complexes have also been screened against HM1:1MSS strains of Entamoeba histolytica.