Enhanced selectivity in green catalytic epoxidation using a supported cobalt complex

Chakrabarty, Rajesh; Das, Barun; Clark, James H.

doi:10.1039/b618862a

Cited by 29 publications

(16 citation statements)

References 34 publications

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“…8,9,12,13 It is also possible to immobilize the complexes on mesoporous silica to obtain stable heterogeneous catalysts for the same reactions. 10,11 In this paper, we discuss the synthesis and physicochemical characteristics of Co(III)-oxo cubane-like clusters of the type Co 4 O 4 (O 2 CR) 4 L 4 . The role of these complexes in catalytic oxidation under homogeneous conditions is also discussed briefly.…”

Section: Introductionmentioning

confidence: 99%

Cobalt(III)-oxo cubane clusters as catalysts for oxidation of organic substrates

Das

Chakrabarty

2011

J Chem Sci

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Transition metal coordination complexes play a vital role as catalysts in the oxidation of organic substrates including renewable chemicals in an economically viable and environmentally friendly way. Here we highlight the preparation, characterization and application of oxo-cubane complexes of cobalt(III) as oxidation catalysts using air and water as oxidants. Cobalt(III)-oxo complexes of the type Co 4 O 4 (O 2 CR) 4 L 4 have been prepared by a general method and these have been characterized by analytical, spectroscopic, electrochemical and crystallographic methods. These soluble complexes have shown promising utility as catalysts in the aerobic oxidation of side chains of alkylaromatic hydrocarbon compounds. Oxidation of neat ethylbenzene has shown very high conversion and selectivity for acetophenone formation. On the other hand, oxidation of p-xylene has been found to yield both p-toluic acid and terephthalic acid. It is also possible to oxidize p-xylene in an aqueous medium under moderate applied O 2 pressure. Selective epoxidation of α-pinene with air as the oxidant also takes place with the cobalt(III)-based homogeneous catalysts.

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Section: Introductionmentioning

confidence: 99%

Cobalt(III)-oxo cubane clusters as catalysts for oxidation of organic substrates

Das

Chakrabarty

2011

J Chem Sci

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“…[11,12] The utilization of molecular oxygen as an oxidant has attracted much interest in the epoxidation of olefins recently, due to its abundance in nature, ease of handling, and lack of toxic byproducts during reaction. [13][14][15][16] Various catalysts have been developed for the aerobic epoxidation of olefins, amongst these are catalysts composed of redox-active transition metals, such as V, [17,18] Mn, [19] Fe, [20][21][22] Co, [23,24] and Cu, [25,26] etc. Most of the current transition-metalbased catalysts (e.g.…”

Section: Introductionmentioning

confidence: 99%

Nanoscaled Copper Metal–Organic Framework (MOF) Based on Carboxylate Ligands as an Efficient Heterogeneous Catalyst for Aerobic Epoxidation of Olefins and Oxidation of Benzylic and Allylic Alcohols

Luan

et al. 2014

Chemistry A European J

122

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Aerobic epoxidation of olefins at a mild reaction temperature has been carried out by using nanomorphology of [Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate) as a high-performance catalyst through a simple synthetic strategy. An aromatic carboxylate ligand was employed to furnish a heterogeneous copper catalyst and also serves as the ligand for enhanced catalytic activities in the catalytic reaction. The utilization of a copper metal-organic framework catalyst was further extended to the aerobic oxidation of aromatic alcohols. The shape and size selectivity of the catalyst in olefin epoxidation and alcohol oxidation was investigated. Furthermore, the as-synthesized copper catalyst can be easily recovered and reused several times without leaching of active species or significant loss of activity.

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“…Various catalysts have been developed for the aerobic epoxidation of olefins, among which are catalysts composed of redox‐active transition metals such as V, Mn, Fe, Co and Cu . However, the vast majority of these catalysts have drawbacks such as difficult separation of the product, as well as deactivation, regeneration and recovery of the catalyst.…”

Section: Introductionmentioning

confidence: 99%

Oxovanadium(IV), copper(II) or cobalt(II) acetylacetone complexes immobilized on amino‐functionalized CMK‐3 for the aerobic epoxidation of styrene

Wang

et al. 2015

Applied Organom Chemis

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*Oxovanadium(IV), copper(II) and cobalt(II) acetylacetone complexes have been grafted onto amino-modified CMK-3-O (VO-NH 2 -CMK-3, Cu-NH 2 -CMK-3 and Co-NH 2 -CMK-3,respectively) and the materials thus prepared were used as heterogeneous catalysts for the aerobic oxidation of styrene. X-ray diffraction, nitrogen adsorption-desorption and transmission electron microscopy measurements confirmed the structural integrity of the mesoporous hosts, and spectroscopic characterization techniques (Fourier transform infrared, X-ray photoelectron, Raman) and thermogravimetry confirmed the ligands and the successful anchoring of the acetylacetone complexes to the modified mesoporous support. VO-NH 2 -CMK-3 displayed a relatively good catalytic performance with 94.6% of styrene conversion using air as oxidant, while Cu-NH 2 -CMK-3 gave 99.6% of styrene conversion using tert-butyl hydroperoxide as oxidant.

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Enhanced selectivity in green catalytic epoxidation using a supported cobalt complex

Abstract: A supported reagent made by immobilising a tetrameric cobalt(III) cubane cluster on mesoporous silica catalyses the aerobic oxidation of a-pinene with enhanced epoxidation selectivity compared with other systems.

Cited by 29 publications

References 34 publications

Cobalt(III)-oxo cubane clusters as catalysts for oxidation of organic substrates

Cobalt(III)-oxo cubane clusters as catalysts for oxidation of organic substrates

Nanoscaled Copper Metal–Organic Framework (MOF) Based on Carboxylate Ligands as an Efficient Heterogeneous Catalyst for Aerobic Epoxidation of Olefins and Oxidation of Benzylic and Allylic Alcohols

Oxovanadium(IV), copper(II) or cobalt(II) acetylacetone complexes immobilized on amino‐functionalized CMK‐3 for the aerobic epoxidation of styrene

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