Alkane Oxygenation with Hydrogen Peroxide Catalysed by Soluble Derivatives of Nickel and Platinum

Shul’pin, Georgiy B.

doi:10.3184/030823402103172257

Cited by 21 publications

(12 citation statements)

References 19 publications

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“…Except cycloketone and cycloalcohol, which are the major products of this reaction, small amounts of cyclohydroperoxide are observed but the formation of ring-opened side-products like di-carboxylic acids is also possible through this mechanism. It is well-known that the selective catalytic oxidation of C-H bonds results in the formation of hydroperoxides [36][37][38]. For the investigated polymolybdates only traces of hydroperoxide (\0.1 %) were detected after 6 h of reaction which is indicative of polymolybdates as good catalysts for hydroperoxides decomposition.…”

Section: Discussionmentioning

confidence: 85%

“…Oxidation of cyclohexane and cyclooctane with hydrogen peroxide as oxygen donor was performed in the presence of the CH 3 ReO 3 -PCA system. Formation of the cycloalkyl hydroperoxide, which was the main product in the cycloalkane oxidation, proceeded via free-radical mechanism [36].…”

Section: Discussionmentioning

confidence: 99%

“…Selective catalytic oxidation of cycloalkanes with molecular oxygen is one of the most important and attractive transformations in organic synthesis [36][37][38]. It is evident that the use of molecular oxygen from air which is an inexpensive, abundant and readily available oxidant in place of other oxygen donors is clearly desirable on economic and environmental grounds.…”

Section: Introductionmentioning

confidence: 99%

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Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen

et al. 2016

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A group of new polymolybdates was synthesized and tested in the catalytic oxidation of cycloalkanes. Investigated compounds exhibit broad structural diversity including polymolybdates with isolated anionic clusters (0-dim), polymeric anions (1-dim), Mo-O layers (2-dim) as well as hexagonal and orthorhombic molybdenum oxides (3-dim). All studied molybdenum complexes were found to be active in the reaction conditions yielding ketones and alcohols as main products. In the case of layered compounds (2-dim), dicarboxylic acid was detected in the mixture of reaction products. The structure of investigated molybdenum compounds was shown to have influence on yields and selectivities of the investigated reactions. Anionic layers separation (in 2-dim materials) as well as type and charge of organic cations present in the compounds are prime examples of structural factors influencing the oxidation reactions efficiencies. On the basis of obtained results and literature reports a mechanism for the oxidation of cycloalkanes by polymolybdates has been proposed. Graphical Abstract

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Section: Discussionmentioning

confidence: 85%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen

et al. 2016

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“…It is known [5,6,8] that the peroxidative oxidation of cyclohexane catalyzed by some derivatives of Mn, Cr, Pd, Pt, Hg, etc. proceeds more efficiently in acidic medium.…”

Section: Effect Of the Amount Of Nitric Acidmentioning

confidence: 99%

Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

Kirillov¹,

Kopylovich²,

Kirillova³

et al. 2006

Adv Synth Catal

167

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Abstract:The mono-, di-, tri-, tetra-and polynuclear copper (II) (5), respectively, are highly active and selective catalysts or catalyst precursors for the peroxidative oxidation of cyclohexane, in acetonitrile, to a cyclohexanol and cyclohexanone mixture, by aqueous hydrogen peroxide in acidic medium (liquid biphasic catalysis) at room temperature and atmospheric pressure. The effects on the catalytic activity of various factors, e.g., the relative amounts of cyclohexane, oxidant, catalyst, solvent and nitric acid, reaction time, catalyst recycling and impact of both carbon-and oxygen-centred radical traps (supporting mainly radical mechanisms) were investigated and allowed us to achieve yields and TONs up to ca. 39% and 380, respectively, corresponding to the most active copper systems so far reported for the oxidation of cyclohexane under mild conditions. The catalysts can be reused for recycling and, at least complex 4 maintains almost the same level of activity even after five reaction cycles. The preparation of the new complexes 1, 2b and 2c by self-assembly at room temperature, and their full characterization by IR spectroscopy, FAB-MS þ , elemental and X-ray diffraction structural (for 1 and 2c) analyses are also reported.

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“…7 and 4 atm, respectively. Since complex 4, with a picolinate ligand, is the most active catalyst and picolinic acid (either incorporated in the catalyst [16] or added as an additive to the reaction mixture) [17,33] is known to enhance strongly the rate of Gif reactions, we also tested in our systems the effect of addition of this free acid. However, no appreciable effect was detected on adding a ten-fold excess (relatively to the catalyst) to the reaction mixture with either the most active complex 4 (compare entry 14 with entry 10, Table 3) or one of the least active ones, compound 1 (compare entry 16 with entry 15).…”

Section: Catalytic Activity Of Rhenium Complexes Towards Ethane Carbomentioning

confidence: 99%

Single-Pot Ethane Carboxylation Catalyzed by New Oxorhenium(V) Complexes with N,O Ligands

Kirillov¹,

Haukka

Kirillova³

et al. 2005

Advanced Synthesis & Catalysis

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The oxorhenium(V) chelates [ReOCl-(N,O-L) (1), in refluxing methanol, with N,N-bis(2-hydroxy-) 2 ], respectively, with ligand esterification in the cases of 3 and 5. All these complexes have been characterized by IR and multinuclear NMR spectroscopy, FAB þ -MS, elemental and X-ray diffraction structural analyses. They act as catalysts, in a single-pot process, for the carboxylation of ethane by CO, in the presence of potassium peroxodisulfate K 2 S 2 O 8 , in trifluoroacetic acid (TFA), to give propionic and acetic acids, in a remarkable yield (up to ca. 30%) and under relatively mild conditions, with some advantages over the industrial processes. The picolinate complex 4 provides the most active catalyst and the carboxylation also occurs, although much less efficiently, by the TFA solvent in the absence of CO. The selectivity can be controlled by the ethane and CO pressures, propionic acid being the dominant product for pressures about ca. 7 and 4 atm, respectively (catalyst 4), whereas lower pressures lead mainly to acetic acid in lower yields. These reactions constitute an unprecedented use of Re complexes as catalysts in alkane functionalization.

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Alkane Oxygenation with Hydrogen Peroxide Catalysed by Soluble Derivatives of Nickel and Platinum

Cited by 21 publications

References 19 publications

Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen

Molybdenum Complexes as Catalysts for the Oxidation of Cycloalkanes with Molecular Oxygen

Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

Single-Pot Ethane Carboxylation Catalyzed by New Oxorhenium(V) Complexes with N,O Ligands

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