Polymer-grafted and neat vanadium(V) complexes as functional mimics of haloperoxidases

Maurya, Mannar R.; Chaudhary, Nikita; Avecilla, Fernando

doi:10.1016/j.poly.2013.09.021

Cited by 39 publications

(18 citation statements)

References 39 publications

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“…Elemental analysis supports results of X-ray measurements, whereas FT-IR spectra of complexes in bulk, in principle very similar, are indicative of coordinated terpyridine [35], with either oxido (1) or dioxido (2) vanadium moieties. Infrared analysis in KBr further proves, that sample powder material does not present any peroxido- [51] or oxido-bridged [48] species, which could imply dimerization of vanadium complexes. There was additional matter that needed to be resolved: were the vanadium oxidation states in the as-synthesized compounds maintained (1 -V(IV), 2 -V(V))?…”

Section: Synthesis Of Complexes 1 Andmentioning

confidence: 78%

New vanadium complexes with 6,6″-dimethyl-2,2′:6′,2″-terpyridine in terms of structure and biological properties

et al. 2015

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Section: Synthesis Of Complexes 1 Andmentioning

confidence: 78%

New vanadium complexes with 6,6″-dimethyl-2,2′:6′,2″-terpyridine in terms of structure and biological properties

et al. 2015

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“…[10] Bromoperoxidases as catalysts for oxidative bromination have been reviewed. [4] A wide variety of vanadium complexes have been synthesized and used as functional models for V-haloperoxidases in order to have a better understanding of the mechanism of action of such enzymes, and these complexes are effective catalyst precursors in various oxidation reactions such as epoxidation of alkenes, oxidation of sulfides, alkanes, arenes and alcohols, as well as in oxidative bromination reactions in the presence of hydrogen peroxide [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] or alkyl hydroperoxides. [26] Inspired by the mechanism of action of V Br PO, a biphasic procedure for bromination reactions was proposed in 1994.…”

Section: Introductionmentioning

confidence: 99%

Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis

et al. 2015

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An efficient three‐component reaction involving carbon monoxide with a range of aryl bromides and N‐substituted acetoacetamides is reported for the synthesis of β‐keto amides. This transformation is promoted by Pd‐catalysis followed by an acid‐mediated deacetylation upon work‐up, enabling a large number of β‐keto amides to be isolated. Finally, d2‐13C‐dyclonine could be synthesized in three steps utilizing the developed catalytic system as the key step.

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“…However, the decrease in product selectivity (%), as well as substrate conversion (%), was observed while using neat catalysts. Surprisingly, catalysts 3–6 show exceptionally high TOF values during the catalytic oxidative bromination of salicylaldehyde . The TOF values of the neat complexes are quite low in comparison to that of grafted catalysts (See Table ).…”

Section: Catalytic Activity Studiesmentioning

confidence: 99%

“…Three major oxidative bromination products i.e. 5‐bromo‐2‐hydroxyl benzaldehyde (5‐BrS), 3‐bromo‐2‐hydroxy benzaldehyde (3‐BrS) and 3, 5‐dibromo‐2‐hydroxybenzaldehyde (3,5‐BrS), were identified during the catalytic reaction (Scheme ) . PS‐[V V O 2 (Haeae‐sal)] ( 5 ) was used as a representative catalyst during the optimization of different reaction parameters namely amount of catalyst, amount of oxidant (30% aqueous H 2 O 2 ), amount of perchloric acid, amount of potassium bromide and amount of solvent, while keeping other reaction conditions such as RPM of magnetic stirrer, size of magnetic bead, shape and size of reaction flask, etc.…”

Section: Catalytic Activity Studiesmentioning

confidence: 99%

Synthesis and characterization of dimeric μ‐oxidovanadium complexes as the functional model of vanadium bromoperoxidase

Maurya

Mahato

Chaudhary

et al. 2020

Applied Organom Chemis

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Two vanadium (IV) complexes [VIVO(Haeae‐sal)(MeOH)]+ (1) and [VIVO(Haeae‐hyap)(MeOH)]+ (2) were prepared by reacting [VO(acac)2] with ligands [H2aeae‐sal] (I) and [H2aeae‐hyap] (II) respectively. Condensation of 2‐(2‐aminoethylamino)ethanol with salicylaldehyde and 2‐hydroxyacetophenone produces the ligands (I) and (II) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid‐state. Single‐crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid‐state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion (TOF value of 2.739 × 102 h−1) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 102 h−1) for the oxidative bromination of salicylaldehyde where 5‐bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 104 h−1 whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 103 h−1 for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.

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Polymer-grafted and neat vanadium(V) complexes as functional mimics of haloperoxidases

Cited by 39 publications

References 39 publications

New vanadium complexes with 6,6″-dimethyl-2,2′:6′,2″-terpyridine in terms of structure and biological properties

New vanadium complexes with 6,6″-dimethyl-2,2′:6′,2″-terpyridine in terms of structure and biological properties

Thymol Bromination – A Comparison between Enzymatic and Chemical Catalysis

Synthesis and characterization of dimeric μ‐oxidovanadium complexes as the functional model of vanadium bromoperoxidase

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