Mechanism of oxidations with H2O2 catalyzed by vanadate anion or oxovanadium(V) triethanolaminate (vanadatrane) in combination with pyrazine-2-carboxylic acid (PCA): Kinetic and DFT studies

Kirillova, Marina V.; Kuznetsov, Maxim L.; Romakh, Vladimir B.; Shul’pina, Lidia S.; Silva, João J. R. Fraústo da; Pombeiro, Armando J. L.; Shul’pin, Georgiy B.

doi:10.1016/j.jcat.2009.08.006

Cited by 152 publications

(51 citation statements)

References 89 publications

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“…Shul'pin and co-workers have observed the same promoting effect in alkane oxidation, when vanadate anions are combined with PCA/H 2 O 2 [31,32]. They produce free HOO • radicals and create V(IV)-species, which are confirmed by DFT calculations [33,34]. We have also obtained an enhancement effect with PCA in the oxidation (O 2 ) of alkanes, catalyzed by supported V and Pd catalysts [24,35,36].…”

Section: Co-catalyst Effectsupporting

confidence: 75%

Selective functionalization of n-hexane with molecular O2 catalyzed by immobilized Cu/Co, Cu/Fe and Co/V complexes on modified Al2O3

Mishra

Kumar

2010

Reac Kinet Mech Cat

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Heterobinuclear macrocyclic complexes, i.e. CuCoL 1, CuFeL 2 and CoVL 3, have been synthesized and anchored onto modified carbamate Al 2 O 3 in order to obtain new hybrid supported catalysts. The identities of the supported metal complexes were confirmed by FT-IR, SEM-EDS and AAS. TGA indicated that the catalysts were thermally stable up to 230°C. These catalysts have been tested for the functionalization of n-hexane with molecular O 2 . The best result was obtained with CuFeL 2 over Al 2 O 3 (ca. 19% overall conversion; 78% selectivity: hexan-2-one plus hexan-2-ol) and promoted conversion could be obtained with 2-pyrazinecarboxylic acid (as co-catalyst). The effects of various factors (temperature, O 2 pressure, reaction time and catalyst concentration) were also investigated in detail. The impact of both C-and O-centred radical traps was also assessed to establish a radical mechanism.

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Section: Co-catalyst Effectsupporting

confidence: 75%

Selective functionalization of n-hexane with molecular O2 catalyzed by immobilized Cu/Co, Cu/Fe and Co/V complexes on modified Al2O3

Mishra

Kumar

2010

Reac Kinet Mech Cat

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“…The [VO 3 ]´/PCA/H 2 O 2 system has been studied in detail [81][82][83][84][85][86][87][88][89][90][91][92]. We then continued studies of alkane oxidations in the presence of PCA under catalysis by complexes of some other metals: iron [93][94][95][96], manganese [97,98], and rhenium [99].…”

Section: Effect Of Additivesmentioning

confidence: 99%

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

174

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This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst). Works of recent years (mainly 2010-2016) devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon-hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.

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“…Contrary to what is generally accepted for the Jacobsen-Katsuki epoxidation, the active epoxidizing agents in the Sharpless process are peroxo, hydro-peroxo or alkyl-peroxo-complexes [104]. Titanium and vanadium appear to bear similar chemical behavior, and both have attracted considerable attention in the last decade [105][106][107][108][109][110]. In general, the coordination sphere in both cases can be quite labile (especially in the case of vanadyl(IV) acetylacetonate, VO(acac) 2 ) [104], which requires additional study of the effect of the different species available during the epoxidation process.…”

Section: Other Epoxidation Catalysts: a Brief Overviewmentioning

confidence: 99%

Strengths, Weaknesses, Opportunities and Threats: Computational Studies of Mn- and Fe-Catalyzed Epoxidations

Teixeira

Cordeiro

2016

Catalysts

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Abstract:The importance of epoxides as synthetic intermediates in a number of highly added-value chemicals, as well as the search for novel and more sustainable chemical processes have brought considerable attention to the catalytic activity of manganese and iron complexes towards the epoxidation of alkenes using non-toxic terminal oxidants. Particular attention has been given to Mn(salen) and Fe(porphyrin) catalysts. While the former attain remarkable enantioselectivity towards the epoxidation of cis-alkenes, the latter also serve as an important model for the behavior of cytochrome P450, thus allowing the exploration of complex biological processes. In this review, a systematic survey of the bibliographical data for the theoretical studies on Mn-and Fe-catalyzed epoxidations is presented. The most interesting patterns and trends are reported and finally analyzed using an evaluation framework similar to the SWOT (Strengths, Weaknesses, Opportunities and Threats) analysis performed in enterprise media, with the ultimate aim to provide an overview of current trends and areas for future exploration.

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Mechanism of oxidations with H2O2 catalyzed by vanadate anion or oxovanadium(V) triethanolaminate (vanadatrane) in combination with pyrazine-2-carboxylic acid (PCA): Kinetic and DFT studies

Cited by 152 publications

References 89 publications

Selective functionalization of n-hexane with molecular O2 catalyzed by immobilized Cu/Co, Cu/Fe and Co/V complexes on modified Al2O3

Selective functionalization of n-hexane with molecular O2 catalyzed by immobilized Cu/Co, Cu/Fe and Co/V complexes on modified Al2O3

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Strengths, Weaknesses, Opportunities and Threats: Computational Studies of Mn- and Fe-Catalyzed Epoxidations

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