Kinetics and mechanism of the osmium tetroxide-catalyzed oxidation of acetone and ethyl methyl ketone by alkaline hexacyanoferrate(III) ion

Singh, Vishwambhar N.; Singh, Hari Shankar; Saxena, B.B.L.

doi:10.1021/ja01038a041

Cited by 37 publications

(7 citation statements)

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“…28,29 There are a number of papers on the kinetics of a variety of organic oxidation reactions with this anion as a catalyst in the presence of a number of co-oxidants. [30][31][32][33] (i ) Oxidation of alcohols, aldehydes, alkyl halides and benzylamines. Solutions of cis-[OsO 4 (OH) 2 ] 2Ϫ were made from OsO 4 and molar aqueous NaOH or KOH.…”

Section: (C) Osomentioning

confidence: 99%

Oxo osmium(VIII) complexes in oxidation: crystal structures of OsO4·nmo (nmo = N-methylmorpholine N-oxide) and OsO4·nmm (nmm = N-methylmorpholine), and use of cis-[OsO4(OH)2]2− as an oxidation catalyst

Bailey¹,

Bhowon²,

Griffith³

et al. 1997

J. Chem. Soc., Dalton Trans.

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The new complexes OsO 4 ؒnmo (nmo = N-methylmorpholine N-oxide) and OsO 4 ؒnmm (nmm = Nmethylmorpholine) have been made, their crystal structures determined, and their possible involvement in the catalysed dihydroxylation of alkenes considered. The use of cis-[OsO 4 (OH) 2 ] 2Ϫ as a catalyst for the oxidation of alcohols, aldehydes and alkyl halides to carboxylic acids with [Fe(CN) 6 ] 3Ϫ and other co-oxidants and also for the cleavage and dihydroxylation of alkenes with [Fe(CN) 6 ] 3Ϫ has been investigated.

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Section: (C) Osomentioning

confidence: 99%

Oxo osmium(VIII) complexes in oxidation: crystal structures of OsO4·nmo (nmo = N-methylmorpholine N-oxide) and OsO4·nmm (nmm = N-methylmorpholine), and use of cis-[OsO4(OH)2]2− as an oxidation catalyst

Bailey¹,

Bhowon²,

Griffith³

et al. 1997

J. Chem. Soc., Dalton Trans.

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“…Homogeneous catalysis by ruthenium and osmium compounds has been reported by several workers but the use of iridium(III) chloride as a homogeneous catalyst in acidic medium has not yet been reported. In the present study it was observed that the average concentration of iridium(III) chloride required to catalyze the oxidation of cycloketones lies in the 10 À6 M range, while at least 10 times higher concentrations of ruthenium(III) chloride with cerium(IV) sulphate in acidic medium [5] and osmium(VIII) oxide with hexacyanoferrate(III) in alkaline medium [6] were required to oxidize various ketones. Herein we report a study of the oxidation of cyclopentanone and 2-methyl cyclohexanone by cerium-(IV) sulphate in aqueous sulphuric acid medium catalyzed by iridium(III) chloride at constant ionic strength of the medium.…”

Section: Introductionmentioning

confidence: 53%

Iridium(III) catalyzed oxidation of cyclic ketones by cerium(IV)

Tandon

Singh

Baboo

et al. 2004

Transition Metal Chemistry

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IrCl 3 which is considered to be a sluggish catalyst in alkaline media, was found to surpass the catalytic efficiency of even osmium and ruthenium in acidic media in the oxidation of cyclopentanone and 2-methylcyclohexanone by cerium(IV) sulphate in aqueous sulphuric acid medium. It was observed that the order of the reaction shows direct proportionality with respect to low concentrations of the oxidant and alcohols, but tends to become independent of concentration at higher concentrations. On increasing the concentrations of externally added Cl À , H þ and Ce III ions, the rate of the reaction decreases sharply initially but the decrease in rate becomes less prominent as their concentration is increased. The rate of reaction is directly proportional with respect to IrCl 3 concentrations. Kinetic data suggest that the production of Ce III ion occurs before the rate-determining step. Parameters such as the energy of activation, free energy of activation and entropy data collected at five different temperatures suggest that cyclopentanone forms the activated complex more easily.

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“…The hexacyanoferrate(III)-hexacyanoferrate(II) system, which has higher redox potential than Cu(II)-Cu(I), substantiates a better possibility for the rapid oxidation of the free radical with hexacyanoferrate(III) in the alkaline medium and the rapid oxidation of the free radicals might completely mask the polymerization. Sometimes the vinyl compounds themselves are oxidized under the experimental conditions used and the test for free radicals fails [32]. In view of less than unit order in [OH -] and also high alkali concentration, the active species of osmium(VIII) is considered as [OsO 5 (OH)] 3- [33], which is shown in prior equilibrium of Scheme 1.…”

Section: Discussionmentioning

confidence: 99%

Mechanistic Studies of Osmium(VIII) Catalysed Oxidation of Sulfanilic Acid by Hexacyanoferrate (III) in Alkaline Medium

Farokhi

Nandibewoor

2008

Catal Lett

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The kinetics of osmium(VIII) catalyzed oxidation of sulfanilic acid (p-aminobenzenesulfonic acid) by hexacyanoferrate(III) (HCF(III)) in alkaline medium was studied spectrophotometrically. The reaction showed first order kinetics in hexacyanoferrate(III) and osmium concentrations and an order of less than unity in sulfanilic acid (SAA) and alkali concentrations. The rate of reaction increased with increase in alkali concentration. Increasing ionic strength and dielectric constant of the medium increased the rate of the reaction. A retarding effect was observed by one of the products i.e. hexacyanoferrate(II) (HCF(II)). A mechanism involving the formation of a complex between sulfanilic acid and osmium(VIII) species, [(OsO 5 (OH)] 3-(in presence of high OH -concentrations), has been proposed. The main products were identified by spectral studies. The reaction constants involved in the mechanism are evaluated.

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Kinetics and mechanism of the osmium tetroxide-catalyzed oxidation of acetone and ethyl methyl ketone by alkaline hexacyanoferrate(III) ion

Cited by 37 publications

References 0 publications

Oxo osmium(VIII) complexes in oxidation: crystal structures of OsO4·nmo (nmo = N-methylmorpholine N-oxide) and OsO4·nmm (nmm = N-methylmorpholine), and use of cis-[OsO4(OH)2]2− as an oxidation catalyst

Oxo osmium(VIII) complexes in oxidation: crystal structures of OsO4·nmo (nmo = N-methylmorpholine N-oxide) and OsO4·nmm (nmm = N-methylmorpholine), and use of cis-[OsO4(OH)2]2− as an oxidation catalyst

Iridium(III) catalyzed oxidation of cyclic ketones by cerium(IV)

Mechanistic Studies of Osmium(VIII) Catalysed Oxidation of Sulfanilic Acid by Hexacyanoferrate (III) in Alkaline Medium

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