Kinetics of Bromide Oxidation by (Oxalato)oxodiperoxomolybdate(VI)

Reynolds, Martha S.; Morandi, Steven J.; Raebiger, James W.; Melican, Sean P.; Smith, Sean P. E.

doi:10.1021/ic00100a022

Cited by 47 publications

(23 citation statements)

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“…A proposed mechanistic scheme which satisfactorily explains the experimental findings, is shown in figure 11. 66 The mechanism is in accord with previous observations that, formation of an oxo-diperoxo configuration [reaction a] may be essential 31,126,154 for a pMo species to be catalytically active in oxidation.…”

Section: Catalytic Activity In Sulfide Oxidationsupporting

confidence: 89%

“…16 Among the various d o transition metal peroxo systems, V(V), Mo(VI) and W(VI), which have clear structural and isoelectronic relationships, attract continuous research attention because of their versatility and selectivity as stoichiometric or catalytic oxidizing or oxo-transfer agent in a variety of organic oxidations such as epoxidation of alkenes, [17][18][19][20] oxidation of sulfides and sulfoxides, [21][22][23][24][25][26] primary and secondary alcohols, 27,28 as well as halide oxidation. [29][30][31][32] Besides these, the active involvement or relevance of these peroxometallates in haloperoxidase, 29,31,32 their insulino-mimetic, [33][34][35][36] anti-neoplastic 37 and enzyme inhibitory activity 38,39 have been well documented. The vanadium-dependent bromoperoxidase (V-BPO) is now the subject of tremendous interest for chemists as well as biologists.…”

Section: Introductionmentioning

confidence: 99%

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Macromolecular peroxo complexes of Vanadium(V) and Molybdenum(VI): Catalytic activities and biochemical relevance

Islam

Boruah

2015

J Chem Sci

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Our recent achievements concerning the synthesis and characterization of water soluble peroxo complexes of V(V) and Mo(VI) in macroligand environment, as well as some key features of biological relevance of these compounds, such as their hydrolytic stability, activity with phosphohydrolase enzyme vis-à-vis free peroxovanadium (pV) or peroxomolybdenum (pMo) complexes, and their activity in biomimetic oxidative bromination are presented here. Immobilization of pMo species on insoluble polymer matrices viz., amino acid functionalized Merrifield resins and poly(acrylonitrile) on the other hand, afforded a set of heterogeneous catalysts highly effective in facile organic transformations such as selective oxidation of organic sulfides and oxidative bromination of aromatic substrates by H 2 O 2 , at ambient temperature. The methodologies are straightforward, high-yielding, halogen-free and the catalysts afford easy regeneration. Our findings illustrate the various features which make the procedures sustainable and synthetically useful.

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Section: Catalytic Activity In Sulfide Oxidationsupporting

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Macromolecular peroxo complexes of Vanadium(V) and Molybdenum(VI): Catalytic activities and biochemical relevance

Islam

Boruah

2015

J Chem Sci

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“…[3][4][5][6][7][8][9][10] They are widely used in stoichiometric as well as catalytic oxidation in organic and biochemistry, 11 for example, in the oxidation of thioanisole, 12,13 methylbenzenes, 14 tertiary amines, alkenes, alcohols, 15,16 bromide 17 and also in olefin epoxidations. [18][19][20][21][22] There has been a continuous upsurge in interest in peroxo compounds of vanadium since it has been demonstrated that vanadate and peroxovanadates are capable of inhibiting the hydrolysis of phosphoproteins [23][24][25][26] and exhibit insulin-like properties.…”

Section: Introductionmentioning

confidence: 99%

Diperoxo Complexes of Vanadium(V) Containing Mannich Base Ligands

et al. 2011

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The vanadium(V) peroxo complexes containing Mannich base ligands having composition Na[VO(O 2 ) 2 (L-L)]•H 2 O [where L-L＝morpholinobenzyl acetamide (MBA), piperidinobenzyl acetamide (PBA), morpholinobenzyl benzamide (MBB), piperidinobenzyl benzamide (PBB), morpholinomethyl benzamide (MMB), piperidinomethyl benzamide (PMB), morpholinobenzyl formamide (MBF), piperdinobenzyl formamide (PBF)] have been reported. The complexes have been prepared by stirring vanadium pentoxide with excess of 30% aqueous-H 2 O 2 followed by treatment with ethanolic solution of the ligand and finally maintained the pH of the reaction mixture by adding dilute solution of sodium hydroxide. The synthesized complexes have been characterized by various physico-chemical techniques, via elemental analysis, molar conductivity, magnetic susceptibility measurements, infra red, electronic, mass, 1 H NMR spectral and TGA/DTA studies. These studies revealed that the synthesized complexes are uni-univalent electrolytes and diamagnetic in nature. The ligands are bound to metal in a bidentate mode through carbonyl oxygen and the ring nitrogen. Thermal analysis result provides conclusive evidence for the presence of one molecule of lattice water in the complexes. Mass spectra confirm the molecular mass of the complexes.

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“…1 They are widely used in stiochiometric as well as catalytic oxidation in organic and biochemistry, 2 for example in the oxidation of thioanisole, 3,4 methylbenzenes, 5 tertiaryamines, alkenes, alcohols, 6,7 bromide 8 and also in olefin epoxidations. [9][10][11][12][13] They also act as isomerisation catalysts for some allylic alcohols and have been applied to bleaching processes.…”

Section: Introductionmentioning

confidence: 99%

Peroxo Complexes of Molybdenum(VI) Containing Mannich Base Ligands

et al. 2009

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The molybdenum(VI)-peroxo complexes containing Mannich base ligands having a formula as [MoO(O 2 [where L-L＝morpholinobenzyl benzamide (MBB), piperidinobenzyl benzamide (PBB), morpholinobenzyl urea (MBU), piperidinobenzyl urea (PBU), morpholinobenzyl thiourea (MBTU), piperdinobenzyl thiourea (PBTU)] have been synthesized and characterized by physico-chemical, electrochemical techniques and TGA/DTA studies. The complexes have been prepared by stirring ammonium molybdate and excess of 30% aqueous-H 2 O 2 and then treatment with ethanolic solution of the ligand. Studies revealed that these complexes were non-electrolytes and diamagnetic in nature. The ligands are bound to metal in a bidentate mode through carbonyl oxygen/thiocarbonyl sulphur and the ring nitrogen. The cyclic voltammograms of the complexes show two quasi-reversible steps involving complexes. The complexes have also been tested for antibacterial activity against Salmonella and Kleibsella. The antibacterial study of the ligands and complexes indicate that the complexes exhibit higher activity than the free ligands.

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Kinetics of Bromide Oxidation by (Oxalato)oxodiperoxomolybdate(VI)

Cited by 47 publications

References 1 publication

Macromolecular peroxo complexes of Vanadium(V) and Molybdenum(VI): Catalytic activities and biochemical relevance

Macromolecular peroxo complexes of Vanadium(V) and Molybdenum(VI): Catalytic activities and biochemical relevance

Diperoxo Complexes of Vanadium(V) Containing Mannich Base Ligands

Peroxo Complexes of Molybdenum(VI) Containing Mannich Base Ligands

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