Vanadium Catalysis in Bromoperoxidation Reaction

Synthesis, characterization, reactivity and antibacterial activity of new peroxovanadium(V) complexes anchored to soluble polymers

“…However, synthetic DPV or monoperoxovanadate or compounds containing such moieties were catalytically incompetent in bromide oxidation at neutral pH [61]. The observation that inactive DPV requires the presence of vanadyl or vanadate to gain oxidant activity at pH >5, led to the proposal that l-peroxo-bridged divanadate intermediate, [OVOOV(O 2 )] 3+ , formed by complexation between these two species is the proximate oxidant of bromide [28]. Support for such an intermediate came from our investigations on a series of synthetic compounds with a VOOV bridge which were found to be active in oxidative bromination at neutral pH [26,27,62].…”

“…(L) 3 ] Á H 2 O (L = amino acid or dipeptide) synthesized by us [26,27] could act as powerful oxidant of bromide with good activity at physiological pH, thus mimicking the enzyme V-BPO. Diperoxovanadate compounds with exclusively peroxo groups in its co-ordination sphere were found to be catalytically incompetent in bromide oxidation at neutral pH [26,28]. The l-peroxo V compounds however, undergo rapid degradation in solution with loss of its high bromination activity.…”

Non-Heme Peroxidases and Catalases: Mechanistic Implications from the Studies of Manganese and Vanadium Model Compounds

“…Similarly, peroxovanadates form monomeric and dimeric species and can bind as many as four peroxides. [57][58][59][60][61][62] Even in the presence of coordinated ligand, dimerization reactions and ligand dissociation often create difficulties.…”

A Dinuclear Peroxo-Vanadium(V) Complex with Coordinated Tripeptide. Synthesis, Spectra and reactivity in Bromoperoxidation

“…The requirement of free vanadate for the DPV-dependent bromination at pH > 5, implied that inactive DPV gains oxidant activity by forming a peroxo-bridged intermediate [OVOOV(O 2 )] 3+ , proposed as a proximate oxidant of bromide. 18 Support for such an intermediate as the bromide oxidant came from our studies on a synthetic compound with a "VOOV" bridge, 21 which could produce a bromination competent intermediate at physiological pH. In order to provide further evidence in confirmation of this potential of bromide oxidation and also in view of the paucity of information on peroxo-bridged divanadate compounds, we were interested in synthesising newer members of such complexes stabilised by biogenic heteroligands, viz, di-and tri-peptides.…”