Catalytic functionalization of methane

Süß‐Fink, Georg; Stanislas, Sandrine; Shul’pin, Georgiy B.; Nizova, G. V.

doi:10.1002/1099-0739(200010)14:10<623::aid-aoc48>3.0.co;2-q

Cited by 29 publications

(8 citation statements)

References 33 publications

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“…246 Under comparable conditions to the hydrocarbon reaction, the vanadium complexes [VO 2 (PCA) 2 ] − and [VO(O 2 )-(PCA) 2 ] − were isolated and characterized (XRD studies) from VO 3 − −PCA−H 2 O 2 247 and were found to have identical reactivity for oxidation of cyclohexane as the precursor VO 3 − − PCA. 248 The authors proposed that the vanadium catalyst functions to activate H 2 O 2 , generating hydroxy radicals which will react with methane to give methyl radicals (Scheme 52). The methyl radicals react with O 2 to generate CH 3 OO • , which can abstract hydrogen from CH 4 to generate the product and another methyl radical which will react further (Scheme 53).…”

Section: Vanadiummentioning

confidence: 99%

Homogeneous Functionalization of Methane

et al. 2017

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One of the remaining "grand challenges" in chemistry is the development of a next generation, less expensive, cleaner process that can allow the vast reserves of methane from natural gas to augment or replace oil as the source of fuels and chemicals. Homogeneous (gas/liquid) systems that convert methane to functionalized products with emphasis on reports after 1995 are reviewed. Gas/solid, bioinorganic, biological, and reaction systems that do not specifically involve methane functionalization are excluded. The various reports are grouped under the main element involved in the direct reactions with methane. Central to the review is classification of the various reports into 12 categories based on both practical considerations and the mechanisms of the elementary reactions with methane. Practical considerations are based on whether or not the system reported can directly or indirectly utilize O as the only net coreactant based only on thermodynamic potentials. Mechanistic classifications are based on whether the elementary reactions with methane proceed by chain or nonchain reactions and with stoichiometric reagents or catalytic species. The nonchain reactions are further classified as CH activation (CHA) or CH oxidation (CHO). The bases for these various classifications are defined. In particular, CHA reactions are defined as elementary reactions with methane that result in a discrete methyl intermediate where the formal oxidation state (FOS) on the carbon remains unchanged at -IV relative to that in methane. In contrast, CHO reactions are defined as elementary reactions with methane where the carbon atom of the product is oxidized and has a FOS less negative than -IV. This review reveals that the bulk of the work in the field is relatively evenly distributed across most of the various areas classified. However, a few areas are only marginally examined, or not examined at all. This review also shows that, while significant scientific progress has been made, greater advances, particularly in developing systems that can utilize O, will be required to develop a practical process that can replace the current energy and capital intensive natural gas conversion process. We believe that this classification scheme will provide the reader with a rapid way to identify systems of interest while providing a deeper appreciation and understanding, both practical and fundamental, of the extensive literature on methane functionalization. The hope is that this could accelerate progress toward meeting this "grand challenge."

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Section: Vanadiummentioning

confidence: 99%

Homogeneous Functionalization of Methane

et al. 2017

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“…Vanadium monoperoxo-complex can function as a ''catalytic pump'' for the generation of hydroxyl radicals [51]. These are very reactive and strong oxidants and promote other radical chains, e.g., by abstracting H from an organic substrate [52].…”

Section: Catalytic Oxidationmentioning

confidence: 99%

Complexes of a diacetylmonoxime Schiff base of S-methyldithiocarbazate (H2damsm) with Fe(III), Ru(III)/Ru(II), and V(IV); catalytic activity and X-ray crystal structure of [Fe(Hdamsm)2]NO3·H2O

El‐Hendawy

Fayed

Mostafa

2011

Transition Met Chem

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The complexes [M(Hdamsm) 2 ]XÁH 2 O (M = Fe, X = NO 3 ; M = Ru, X = Cl), [Ru(Hdamsm)(PPh 3 ) 2 X 0 ] (X 0 = Cl, Br), and [VO(Hdamsm)(acac)] (H 2 damsm = diacetylmonoxime Schiff base of S-methyldithiocarbazate, Hacac = acetylacetone) have been prepared and characterized by spectroscopic techniques. Their redox properties were investigated by cyclic voltammetry. The X-ray crystal structure of [Fe(Hdamsm) 2 ]NO 3 .H 2 O has been determined and shows that the complex has a distorted octahedral geometry in which the Hdamsm behaves as a monoanionic NNS tridentate ligand coordinating via oxime nitrogen, hydrazinic imine nitrogen, and thiolate sulfur. The reactivity of these complexes toward oxidation of alcohols in the presence of t-BuOOH and H 2 O 2 as co-oxidants is reported.

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“…Many oxidants, such as H 2 O 2 [17][18][19][20][21][22][23][24][25][26][27][28][29][30] , benzoyl peroxide [31,32] , tert-butyl hydroperoxide(t-BuOOH) [32,33] , m-chloroperoxybenzoic acid [32] , urea-hydrogen peroxide adduct [32] , K 2 S 2 O 8 [31] and (NH 4 ) 2 S 2 O 8 [31] have been investigated for Cy oxidation. Among them, H 2 O 2 is particularly attractive as it is cheap, reasonably stable and readily available, gives only water as by-product, and always behaves as the most effective oxidizing agent.…”

Section: Effect Of the Amount Of H 2 Omentioning

confidence: 99%

Investigation into experimental conditions and factors for cyclohexane oxidation with VO(acac)2

Xing

et al. 2014

Chem. Res. Chin. Univ.

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The catalytic activity of VO(acac) 2 for the cyclohexane(Cy) oxidation was studied. The effects of various parameters, such as the amounts of H 2 O 2 , HNO 3 , H 2 O and Cy were investigated. The highest total turnover number(TON) is 234, which can be increased to 353, 342 and 403, respectively with the adding of o-phthalic, m-phthalic or p-phthalic acid. A reaction mechanism was also supposed primarily.

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Catalytic functionalization of methane

Abstract: À (3). The implications of these species in the catalytic process are discussed.

Cited by 29 publications

References 33 publications

Homogeneous Functionalization of Methane

Homogeneous Functionalization of Methane

Complexes of a diacetylmonoxime Schiff base of S-methyldithiocarbazate (H2damsm) with Fe(III), Ru(III)/Ru(II), and V(IV); catalytic activity and X-ray crystal structure of [Fe(Hdamsm)2]NO3·H2O

Investigation into experimental conditions and factors for cyclohexane oxidation with VO(acac)2

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