Oxidation of Glycerol with Hydrogen Peroxide Catalyzed by Metal Complexes

Mandelli, Dalmo; Carvalho, Wagner A.; Shul’pina, Lidia S.; Kirillov, Alexander M.; Kirillova, Marina V.; Pombeiro, Armando J. L.; Shul’pin, Georgiy B.

doi:10.1002/9781118742952.ch19

Cited by 3 publications

(2 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…4 Explanations are conceivable. For example, glycerol may be more than a cosolvent 83 by behaving as a reducing agent 84,85 to favor the formation of the less oxidized heterovalent dimer 3a. Reactivity Comparisons of TAML Species.…”

Section: Comparison Of Initial Rates Of Nadh Oxidationmentioning

confidence: 99%

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IV Dimer and Associated Catalytic Chemistry

et al. 2015

View full text Add to dashboard Cite

Iron TAML activators of peroxides are functional catalase-peroxidase mimics. Switching from hydrogen peroxide (H2O2) to dioxygen (O2) as the primary oxidant was achieved by using a system of reverse micelles of Aerosol OT (AOT) in n-octane. Hydrophilic TAML activators are localized in the aqueous microreactors of reverse micelles where water is present in much lower abundance than in bulk water. n-Octane serves as a proximate reservoir supplying O2 to result in partial oxidation of FeIII to FeIV-containing species, mostly the FeIIIFeIV (major) and FeIVFeIV (minor) dimers which coexist with the FeIII TAML monomeric species. The speciation depends on the pH and the degree of hydration w0, viz., the amount of water in the reverse micelles. The previously unknown FeIIIFeIV dimer has been characterized by UV–vis, EPR, and Mössbauer spectroscopies. Reactive electron donors such as NADH, pinacyanol chloride, and hydroquinone undergo the TAML-catalyzed oxidation by O2. The oxidation of NADH, studied in most detail, is much faster at the lowest degree of hydration w0 (in “drier micelles”) and is accelerated by light through NADH photochemistry. Dyes that are more resistant to oxidation than pinacyanol chloride (Orange II, Safranine O) are not oxidized in the reverse micellar media. Despite the limitation of low reactivity, the new systems highlight an encouraging step in replacing TAML peroxidase-like chemistry with more attractive dioxygen-activation chemistry.

show abstract

Section: Comparison Of Initial Rates Of Nadh Oxidationmentioning

confidence: 99%

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IV Dimer and Associated Catalytic Chemistry

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Various vanadium derivatives are known to catalyze the oxidations of organic compounds with inorganic and organic peroxides (see reviews [18,19] and original papers [20][21][22]). Most oxidovanadium(IV) complexes have monomeric structures with an octahedral or square-pyramidal coordination geometry of vanadium [23][24][25][26][27][28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

et al. 2019

View full text Add to dashboard Cite

Reactions of [VCl3(thf)3] or VBr3 with 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) in a 1:1 molar ratio in air under solventothermal conditions has afforded polymeric oxidovanadium(IV) four complexes 1–4 of a general formula [VO(L)X2]n (L = bpy, phen and X = Cl, Br). Monomeric complex [VO(DMF)(phen)Br2] (4a) has been obtained by the treatment of compound 4 with DMF. The complexes were characterized by IR spectroscopy and elemental analysis. The crystal structures of 3 and 4a were determined by an X-ray diffraction (XRD) analysis. The {VOBr2(bpy)} fragments in 3 form infinite chains due to the V = O…V interactions. The vanadium atom has a distorted octahedral coordination environment. Complexes 1–4 have been tested as catalysts in the homogeneous oxidation of alkanes (to produce corresponding alkyl hydroperoxides which can be easily reduced to alcohols by PPh3) and alcohols (to corresponding ketones) with H2O2 or tert-butyl hydroperoxide in MeCN. Compound 1 exhibited the highest activity. The mechanism of alkane oxidation was established using experimental selectivity and kinetic data and theoretical DFT calculations. The mechanism is of the Fenton type involving the generation of HO• radicals.

show abstract

Enhancing the biodiesel manufacturing process by use of glycerin to produce hyacinth fragrance

Silva

Figueiredo

Rodrigues

et al. 2016

Clean Techn Environ Policy

View full text Add to dashboard Cite

Oxidation of Glycerol with Hydrogen Peroxide Catalyzed by Metal Complexes

Cited by 3 publications

References 60 publications

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IV Dimer and Associated Catalytic Chemistry

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IV Dimer and Associated Catalytic Chemistry

New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

Enhancing the biodiesel manufacturing process by use of glycerin to produce hyacinth fragrance

Contact Info

Product

Resources

About

Oxidation of Glycerol with Hydrogen Peroxide Catalyzed by Metal Complexes

Cited by 3 publications

References 60 publications

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an FeIIIFeIV Dimer and Associated Catalytic Chemistry

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an FeIIIFeIV Dimer and Associated Catalytic Chemistry

New Oxidovanadium(IV) Complexes with 2,2′-bipyridine and 1,10-phenathroline Ligands: Synthesis, Structure and High Catalytic Activity in Oxidations of Alkanes and Alcohols with Peroxides

Enhancing the biodiesel manufacturing process by use of glycerin to produce hyacinth fragrance

Contact Info

Product

Resources

About

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IV Dimer and Associated Catalytic Chemistry

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IV Dimer and Associated Catalytic Chemistry