Role of alkylperoxo complexes of cobalt (III) in catalytic oxidation of cyclohexane by cumene hydroperoxide in the presence of bis (acetylacetonato) cobalt (II)

Talsi, Evgenii P.; Chinakov, V. D.; Babenko, V. P.; Sidelnikov, V. N.; Zamaraev, K. I.

doi:10.1016/0304-5102(93)80008-i

Cited by 32 publications

(33 citation statements)

References 23 publications

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“…Results of studies on alkane oxidation and olefin epoxidation by us 4,5 and others 7,15,22,25 now indicate that when the [L n Co III -OOR] species comprise strong-field ligand(s) L (thus stabilizing the +3 oxidation state), homolysis of the O-O bond in the Co-OOR moiety is favored. These [L n Co III -OOR] complexes therefore afford RO • radicals in solution and promote alkane oxidation.…”

Section: Structures Of [Co(acac) 2 (Py)(oo T Bu)] (1) and [Co(acac) 2mentioning

confidence: 88%

“…In the later report, the relevance of [Co(acac) 2 (py)(OOR)] species in the oxidation of hydrocarbons in reaction mixtures consisting of [Co(acac) 2 ]/PhCMe 2 OOH/pyridine has been discussed. 7 A close scrutiny of the literature, however, reveals that, to date, no systematic study has been carried out to assess the ability of [Co( -diketonate) 2 (L)OOR] complexes to catalyze oxidation of hydrocarbons. Furthermore, no [Co( -diketonate) 2 (L)OOR] species has been characterized by X-ray crystallography.…”

Section: Introductionmentioning

confidence: 98%

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Syntheses and Stuctures of Alkyl Peroxo Adducts of β-Diketonate Cobalt(III) Complexes and Their Role in Oxidation of Hydrocarbons and Olefin Epoxidation

et al. 1999

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To assess the oxidizing capacity of [Co( -diketonate) 2 (L)OOR] complexes, four such species, namely, [Co-(acac) 2 (L)(OO t Bu)] (acacH ) acetylacetone; L ) pyridine (py) (1), 4-methylpyridine (4-Mepy) (2), 1-methylimidazole (1-MeIm) (3)) and [Co(dbm) 2 (py)(OO t Bu)] (4, dbmH ) dibenzoylmethane), have been synthesized and the structures of 1, 3, and 4 have been determined by X-ray crystallography. Complex 1 crystallizes in the triclinic space group P1 h with a ) 9.149(2) Å, b ) 9.741(2) Å, c ) 13.067 (2) Å, R ) 84.22 (2)°, ) 77.89(2)°, γ ) 67.83(2)°, V ) 1054.1(4) Å 3 , and Z ) 2. Complex 3 crystallizes in the monoclinic space group P2 1 /n with a ) 11.341(2) Å, b ) 10.485(2) Å, c ) 18.863(2) Å, R ) 90°, ) 106.230(15)°, γ ) 90°, V ) 2153.6(8) Å 3 , and Z ) 4. Complex 4‚1.5C 6 H 6 crystallizes in the monoclinic space group P2 1 /c with a ) 14.907(5) Å, b ) 18.701-(5) Å, c ) 15.207(4) Å, R ) 90°, ) 103.52 (2)°, γ ) 90°, V ) 4122(2) Å 3 , and Z ) 4. The geometry around the Co(III) center in all four complexes is distorted octahedral, and the two -diketonate ligands are cis to each other. The Co-O and O-O bond distances in the Co-OO t Bu moiety fall in the narrow ranges of 1.860(3)-1.879 (2) and 1.451(3)-1.466(3) Å, respectively. Although stable in the solid state, these complexes decompose in benzene or halocarbon solutions to afford t BuOO • and t BuO • radicals. When alkanes like cyclohexane are present in the reaction mixture, these radicals initiate oxidation of the C-H bond. The oxidizing capacity follows the order 1 > 2 > 3 > 4. Decomposition of the complexes in the presence of cyclohexene and an aldehyde results in selective epoxidation in high yield.

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Section: Structures Of [Co(acac) 2 (Py)(oo T Bu)] (1) and [Co(acac) 2mentioning

confidence: 88%

Section: Introductionmentioning

confidence: 98%

Syntheses and Stuctures of Alkyl Peroxo Adducts of β-Diketonate Cobalt(III) Complexes and Their Role in Oxidation of Hydrocarbons and Olefin Epoxidation

et al. 1999

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“…A decade ago, following the discovery [5,6] of molecular sieve titanosilicates such as TS-1, it was reported [7,8] that nhexane yielded a mixture of four products when hydrogen peroxide was used as the oxidant for the selective oxidation catalyzed by TS-1: 2-hexanol (17 %), 3-hexanol (39 %), 2-hexanone (34 %), and 3-hexanone (10 %). In a series of recent papers [9±13] we have reported how aluminophosphate (AlPO) molecular sieves, which contain an appropriate, framework-substituted transition-metal ion, M, in a high oxidation state, serve as effective catalysts for the selective oxidation of alkanes (especially at the terminal position).…”

Section: Methodsmentioning

confidence: 99%

“…The latter compound is generated from cyclohexane using homogeneous (cobaltbased) catalysts, often in combination with promoters and peroxides. [2±4] Alternative synthetic routes have been developed, such as the one-step oxidation of cyclohexane with either alkyl hydroperoxide as oxidant and a catalyst consisting of cobalt salts [5,6] or dioxygen as oxidant and a cobalt acetate catalyst in acetic acid. [7] More recent industrial syntheses include the homogeneously catalysed hydrocarboxylation [8,9] or carboalkoxylation [10] of butadiene.…”

mentioning

confidence: 99%

Designing a Heterogeneous Catalyst for the Production of Adipic Acid by Aerial Oxidation of Cyclohexane

Dugal¹,

Sankar²,

Raja³

et al. 2000

Angew. Chem. Int. Ed.

190

138

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“…As a result, alternative synthetic routes have been developed for one-step oxidation of cyclohexane with either alkyl hydroperoxides or dioxygen in liquid phase [1][2][3][4]. Noticeably, Thomas et al have recently demonstrated a smart approach using a single site designed framework-containing Fe III AlPO-31 catalyst which can give 65% selectivity towards adipic acid under aerial oxidation conditions [4].…”

Section: Introductionmentioning

confidence: 98%

Selective oxidation of cyclohexane in supercritical carbon dioxide

Abutaki

Zhou

et al. 2007

Catal Lett

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A feasibility study into the novel concept of using molecular oxygen to carry out one-step catalytic oxidation of cyclohexane to adipic acid in supercritical carbon dioxide over two types of catalysts, namely Co 2þ =Mn 2þ =NaBr and Ag polyoxometallate, the silver decamolybdodivanadophosphate ðAg 5 PMo 10 V 2 O 40 Þ was carried out. Poor activity and selectivity towards adipic acid were initially noted over the aqueous micellar Co 2þ =Mn 2þ =NaBr catalyst for the cyclohexane oxidation in supercritical carbon dioxide while under comparable conditions, the same catalyst gave a high activity for alkylaromatics oxidation to corresponding acids. It was later found that the adipic acid, being the extremely polar oxidised products, was virtually insoluble in the supercritical phase, which was rapidly degraded to carbon oxides after its prolonged contact with catalyst and O 2 . Thus, the one-step cyclohexane oxidation to adipic acid with good selectivity can only be achieved by modifying the solvent with acetic acid or methanol, which enabled isolation of the acid from further oxidation. On the other hand, Ag 5 PMo 10 V 2 O 40 , in methanol modified supercritical carbon dioxide gave an impressive selectivity for cyclohexane conversion to other oxygenates.

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Role of alkylperoxo complexes of cobalt (III) in catalytic oxidation of cyclohexane by cumene hydroperoxide in the presence of bis (acetylacetonato) cobalt (II)

Cited by 32 publications

References 23 publications

Syntheses and Stuctures of Alkyl Peroxo Adducts of β-Diketonate Cobalt(III) Complexes and Their Role in Oxidation of Hydrocarbons and Olefin Epoxidation

Syntheses and Stuctures of Alkyl Peroxo Adducts of β-Diketonate Cobalt(III) Complexes and Their Role in Oxidation of Hydrocarbons and Olefin Epoxidation

Designing a Heterogeneous Catalyst for the Production of Adipic Acid by Aerial Oxidation of Cyclohexane

Selective oxidation of cyclohexane in supercritical carbon dioxide

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