Oxidation of ketones by ceric perchlorate catalysed by iridium(III)

Tandon, Praveen K.; Sahgal, Sumita; Singh, Alok Kumar; Gayatri,; Purwar, Manisha

doi:10.1016/j.molcata.2005.01.031

Cited by 18 publications

(10 citation statements)

References 13 publications

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“…Homogeneous catalysis by iridium(III) chloride has been given little attention due to its sluggish catalytic activity in alkaline media [2,3]. However, we have reported powerful catalytic activity for the iridium(III)-cerium(IV) system in acidic medium in the oxidation of aliphatic ketones [4][5][6].…”

Section: Introductionmentioning

confidence: 98%

Kinetics of iridium(III) catalyzed oxidation of benzaldehyde and p-nitrobenzaldehyde by cerium(IV) in aqueous acidic medium

Tandon

Purwar

Dwivedi

et al. 2008

Transition Met Chem

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Oxidation of benzaldehyde and p-nitrobenzaldehyde by cerium(IV) sulphate in aqueous sulphuric acid is strongly catalyzed by iridium(III) chloride. The complex formed between cerium(IV) and the organic substrate in the first equilibrium step gives another complex in the presence of iridium(III), which ultimately gives the corresponding aromatic acids as the product of oxidation. The order of the reaction follows first-order kinetics at low concentrations to zero order at higher concentrations of both the oxidant and organic substrate. The rate is directly proportional to the concentration of catalyst, but decreases sharply with increasing H + ions and cerium(III) concentrations, while change in ionic strength of the medium or the concentration of acetic acid and Cl -ions has no effect on the rate.

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Section: Introductionmentioning

confidence: 98%

Kinetics of iridium(III) catalyzed oxidation of benzaldehyde and p-nitrobenzaldehyde by cerium(IV) in aqueous acidic medium

Tandon

Purwar

Dwivedi

et al. 2008

Transition Met Chem

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“…UV-Visible spectral study we get the complex formed between the organic substrate and oxidant. During the kinetics study of oxidation of cyclic alcohols, aromatic aldehydes and aromatic hydrocarbons we observed [35][36][37] that the complex formed cerium(IV) with organic substrate in the first step. Ce(IV), Mn(III), Co(III) and V(V) in one -equivalent oxidant that remove one electron at a time from the substrate it undergo generate anionic, cation radicals or free radicals 38 neutral or anionic organic species, cation radicals or free radicals are generated.…”

Section: Nmr: δ 7124-7719 (8h M)mentioning

confidence: 99%

Au(iii) and Cu(ii) Catalyst for Oxidation of Aromatic and Cyclic Hydrocarbon by Cerium (Iv) in Acidic Medium Under Microwave Irradiation

Srivastava

Goyal²,

Srivastava³

et al. 2016

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The addition of traces of Au(III) chloride with Ce(IV) sulphate (catalyst: substrate ratio (1: 80 to 1: 300)) and in case of Cu(II) sulphate with Ce(IV) sulphate(catalyst: substrate ratio (1: 60 to 1: 250)) in solution phase under microwave irradiation resulted in good to excellent yields of corresponding to phenol, quinone and carbonyl compounds. In case of oxidation of anthracene, phenanthrene, naphthalene, cyclohexane and toluene dissolved in acetic acid to give 95.02 %, 85.25%, 34.68%, 40.94%, and 56.54% yields in case of gold catalyst and 93.5%, 83.4%, 24.68%, 38.25% and 47.11% yields in case of copper as a catalyst. Phenanthrene was oxidized in 9-Fluorenone instead of phenanthraquinone to get the benzylic rearrangement.

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“…Cerium(IV) has been reported to oxidize various aromatic compounds having different functional groups, but these oxidations have been studied mainly from the synthetic point of view. Kinetic study of the catalyzed oxidation of various aliphatic organic compounds by cerium(IV) like alcohols and ketones [2][3][4][5] has been reported by us. We have also reported the oxidation of cyclic ketones by alkaline hexacyanoferrate(III) catalyzed by rhodium(III) chloride, in which it was observed that the catalytically active species of rhodium(III) depends on the pH of the medium [6,7].…”

Section: Introductionmentioning

confidence: 99%

Oxidation of Vicinal Diols by Cerium(IV) in Aqueous Acidic Media Catalyzed by Rhodium(III)

Tandon¹

2012

TOCATJ

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Potential of rhodium(III) chloride in catalyzing, in aqueous sulfuric acid medium, the oxidation of vicinal diols, and the kinetics of reaction of cerium(IV) with propane-1,2-diol and butane-2,3-diol catalyzed by rhodium(III) chloride was investigated. Data show that the reactions follow first order kinetics with respect to low cerium(IV) for lower concentrations, but a further increase in the oxidant concentration retards the reaction velocity. The reaction rate shows direct proportionality with respect to low concentrations of diol, which tends to become zero order at higher concentrations of the organic substrate. The Rate is first order in catalyst. Increase in the concentrations of hydrogen and cerium(III) ions show retarding effects while increase in chloride ion concentration and in turn ionic strength of the medium has a positive effect on the rate. Stoichiometry and spectral studies confirmed the formation of one molecule each of formaldehyde and acetaldehyde and two molecules of acetaldehyde as the products of oxidation in case of propane-1,2-diol and butane-2,3-diol respectively. Thermodynamic parameters like enthalpy of activation, free energy of activation and entropy values were calculated and it was found that the formation of activated complex in the case of butane-2,3-diol was easy compared to that in the case of propane-1,2-diol.

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Oxidation of ketones by ceric perchlorate catalysed by iridium(III)

Cited by 18 publications

References 13 publications

Kinetics of iridium(III) catalyzed oxidation of benzaldehyde and p-nitrobenzaldehyde by cerium(IV) in aqueous acidic medium

Kinetics of iridium(III) catalyzed oxidation of benzaldehyde and p-nitrobenzaldehyde by cerium(IV) in aqueous acidic medium

Au(iii) and Cu(ii) Catalyst for Oxidation of Aromatic and Cyclic Hydrocarbon by Cerium (Iv) in Acidic Medium Under Microwave Irradiation

Oxidation of Vicinal Diols by Cerium(IV) in Aqueous Acidic Media Catalyzed by Rhodium(III)

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