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Reaction between [VO(acac)(2)] and the ONN donor Schiff base Hsal-ambmz (I) (Hsal-ambmz = Schiff base obtained by the condensation of salicylaldehyde and 2-aminomethylbenzimidazole) resulted in the formation of the complexes [V(IV)O(acac)(sal-ambmz)] (1), [V(V)O(2)(acac-ambmz)] (2) (Hacac-ambmz = Schiff base derived from acetylacetone and 2-aminomethylbenzimidazole), and the known complex [V(IV)O(sal-phen)] (3) (H(2)sal-phen = Schiff base derived from salicylaldehyde and o-phenylenediamine). Similarly, [V(IV)O(acac)(sal-aebmz)] (7) has been isolated from the reaction with Hsal-aebmz (II) (Hsal-aebmz derived from salicylaldehyde and 2-aminoethylbenzimidazole). Aerial oxidation of the methanolic solutions/suspensions of 1 and 7 yielded the dioxovanadium(V) complexes [V(V)O(2)(sal-ambmz)] (4) and [V(V)O(2)(sal-aebmz)] (8), respectively. Reaction of VOSO(4) with II gave [{V(IV)O(sal-aebmz)}(2)SO(4)] (9) and [V(IV)O(sal-aebmz)(2)] (10), along with 3 and 8. Under similar reaction conditions, I gave only [{V(IV)O(sal-ambmz)}(2)SO(4)] (5) and 3 as major products. Treatment of 1 and 7 with benzohydroxamic acid (Hbha) yielded the mixed-chelate complexes [V(V)O(bha)(sal-ambmz)] (6) and [V(V)O(bha)(sal-aebmz)] (11). The crystal and molecular structures of 2, 3.1/2DMF, 7.1/4H(2)O, 8, 9.2H(2)O, 10, and 11 have been determined, confirming the ONN binding mode of the ligands. In complex 10, one of the ligands is coordinated through the azomethine nitrogen and phenolate oxygen only, leaving the benzimidazole group free. In the dinuclear complex 9, bridging functions are the phenolate oxygens from both of the ligands and two oxygens of the sulfato group. The unstable oxoperoxovanadium(V) complex [V(V)O(O(2))(sal-aebmz)] (12) has been prepared by treatment of 7 with aqueous H(2)O(2). Acidification of methanolic solutions of 7 and 10 lead to (reversible) protonation of the bemzimidazole, while 8 was converted to an oxo-hydroxo species. Complexes 2, 4, and 8 catalyze the oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide and methyl phenyl sulfone, a reaction mimicking the sulfideperoxidase activity of vanadate-dependent haloperoxidases. These complexes are also catalytically active in the oxidation of styrene to styrene oxide, benzaldehyde, benzoic acid, and 1-phenylethane-1,2-diol.