Homo- and heterometallic polynuclear transition metal catalysts for alkane C H bonds oxidative functionalization: Recent advances

Nesterov, Dmytro S.; Nesterova, Oksana V.; Pombeiro, Armando J. L.

doi:10.1016/j.ccr.2017.08.009

Cited by 120 publications

(81 citation statements)

References 158 publications

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“…Oxidation of hydrocarbons is a key challenge in petrochemical industrial processes due to the efficient conversion from cheap petroleum feed stocks to value-added oxygenated compounds (Liao et al 2014, Labinger 2016, Silva et al 2017, Nesterov et al 2018, Xu et al 2018. Oxidation of cumene into 2-phenyl-2propanol (Ph-PrOH) and acetophenone (Ph = O) is one of such reactions.…”

Section: Introductionmentioning

confidence: 99%

Selective oxidation of cumene into 2-phenyl-2-propanol and acetophenone over activated carbon supported Co_1.5PW₁₂O₄₀ material

Abduh

AlGarni

Kahtani

et al. 2020

Mater. Res. Express

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This article reports the oxidation of cumene by H 2 O 2 in the presence of CO 2 . It describes the role played by carbon dioxide on the course of the reaction. The reaction was catalyzed by unsupported Co 1.5 PW 12 O 40 and supported on activated carbon. The prepared materials were characterized by ICP, IR, XRD and UV. Analysis of the reaction products by gas chromatography coupled with mass spectrometry and gas chromatography showed that 2-phenyl-2-propanol and acetophenone were the main products of the reaction. Activated carbon significantly increases conversion by increasing Co 1.5 PW 12 O 40 accessibility to cumene molecules. The improvement in the conversion and selectivities of 2-phenyl-2-propanol and acetophenone by the use of the oxidizing system H 2 O 2 /CO 2 compared to the use of H 2 O 2 alone or CO 2 alone is due to the role of the percarbonate entity -HCO 4 formed by reaction between H 2 O 2 and CO 2 . Oxidation by large amounts of H 2 O 2 decreases the conversion by decreasing the solubility of cumene in the resulting aqueous medium. An increase in the reaction time resulting in a decrease in the concentration of H 2 O 2 and leaving the effect of the predominant CO 2 accentuates the cracking reactions.

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Section: Introductionmentioning

confidence: 99%

Selective oxidation of cumene into 2-phenyl-2-propanol and acetophenone over activated carbon supported Co_1.5PW₁₂O₄₀ material

Abduh

AlGarni

Kahtani

et al. 2020

Mater. Res. Express

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“…Selective transformation of inactive aliphatic C−H bonds into suitable functional groups is a principal goal of modern chemistry [1][2][3][4][5][6][7][8]. Among the already developed approaches towards the C-H activation, those capable of selective insertion of oxygen into a particular sp 3 carbon-hydrogen bond are less numerous and often are limited to specific positions (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…We recently reported a cobalt complex with a simple N,O-donor isoindole ligand, which revealed a high stereoselectivity in the course of oxidation of sp 3 C-H bonds using m-chloroperoxybenzoic acid (m-CPBA) oxidant [26]. Being interested in better understanding of the mechanism of the retention of stereoconfiguration and following our long-term interest in polynuclear coordination compounds [2,27], we have prepared a novel cobalt complex bearing a similar N,O-donor ligand, but decorated with a second redox inactive metal, [Co III Zn II L 3 Cl 2 ]•CH 3 OH (1) (HL = 2-methoxy-6-[(methylimino)methyl]phenol, Scheme 1). It was recently shown that non-redox metals, such as zinc, cadmium, bismuth etc., may influence the redox reaction pathway or even serve as the main catalysts [28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Heterometallic CoIIIZnII Schiff Base Catalyst for Mild Hydroxylation of C(sp3)–H Bonds of Unactivated Alkanes: Evidence for Dual Mechanism Controlled by the Promoter

et al. 2019

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The novel Schiff base complex [CoIIIZnIIL3Cl2]·CH3OH (1) was synthesized by interaction of zinc powder, cobalt(II) chloride and methanol solution of the pre-formed HL in air (HL is the product of condensation of o-vanillin and methylamine) and characterized by IR, UV-Vis and NMR spectroscopy, ESI-MS and single crystal X-ray diffraction analysis. In the heterometallic core of 1 the two metal centers are bridged by deprotonated phenoxy groups of the L− ligands with the cobalt-zinc separation of 3.123 Å. Catalytic investigations demonstrated a pronounced activity of 1 towards mild alkane oxidation with m-chloroperbenzoic acid (m-CPBA) as an oxidant and cis-1,2-dimethylcyclohexane (cis-1,2-DMCH) as the model substrate. The influence of the nature of different promoting agents of various acidities (from HOTf to pyridine) on the catalytic process was studied in detail and a pronounced activity of 1 in the presence of nitric acid promoter was found, also showing a high retention of stereoconfiguration of the substrate (>99% for cis-1,2-DMCH). The best achieved yield of tertiary cis-alcohol based on the oxidant was 61%, with a turnover number (TON) of 198 for nitric acid as promoter. The 18O-incorporations into the alcohols when the reactions were performed under 18O2 atmosphere using acetic and nitric acid promoters, suggest that the cis-1,2-DMCH hydroxylation proceeds by two distinct pathways, a non-stereoselective and a stereoselective one (with and without involvement of a long-lived free carbon radical, respectively). The former dominates in the case of acetic acid promoter and the latter is realized in the case of HNO3 promoter.

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“…The process has a strong foundation in understanding enzymatic oxygenation of hydrocarbons. [1][2][3][4][5][6][7] Cytochrome P450 and peroxidase enzymes react aerobically through high-oxidation-state iron oxo (Fe IV =O, "ferryl heme") complexes. [8][9][10] Tyrosinase enzymes feature bimetallic Cu I active sites that oxidize catechol to ortho-quinone.…”

Section: Introductionmentioning

confidence: 99%

Earth-Abundant Mixed-Metal Catalysts for Hydrocarbon Oxygenation

et al. 2018

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The oxygenation of aliphatic and aromatic hydrocarbons using earth-abundant Fe and Cu catalysts and "green" oxidants such as hydrogen peroxide is becoming increasingly important to atom-economical chemical processing. In light of this, we describe that dinuclear Cu complexes of pyrrolic Schiff-base macrocycles, in combination with ferric chloride (FeCl), catalyze the oxygenation of π-activated benzylic substrates with hydroperoxide oxidants at room temperature and low loadings, representing a novel design in oxidation catalysis. Mass spectrometry and extended X-ray absorption fine structure analysis indicate that a cooperative action between Cu and Fe occurs, most likely because of the interaction of FeCl or FeCl with the dinuclear Cu macrocycle. Voltammetric measurements highlight a modulation of both Cu and Fe redox potentials in this adduct, but electron paramagnetic resonance spectroscopy indicates that any Cu-Fe intermetallic interaction is weak. High ketone/alcohol product ratios, a small reaction constant (Hammett analysis), and small kinetic isotope effect for H-atom abstraction point toward a free-radical reaction. However, the lack of reactivity with cyclohexane, oxidation of 9,10-dihydroanthracene, oxygenation by the hydroperoxide MPPH (radical mechanistic probe), and oxygenation in dinitrogen-purge experiments indicate a metal-based reaction. Through detailed reaction monitoring and associated kinetic modeling, a network of oxidation pathways is proposed that includes "well-disguised" radical chemistry via the formation of metal-associated radical intermediates.

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Homo- and heterometallic polynuclear transition metal catalysts for alkane C H bonds oxidative functionalization: Recent advances

Cited by 120 publications

References 158 publications

Selective oxidation of cumene into 2-phenyl-2-propanol and acetophenone over activated carbon supported Co_1.5PW₁₂O₄₀ material

Selective oxidation of cumene into 2-phenyl-2-propanol and acetophenone over activated carbon supported Co_1.5PW₁₂O₄₀ material

Heterometallic CoIIIZnII Schiff Base Catalyst for Mild Hydroxylation of C(sp3)–H Bonds of Unactivated Alkanes: Evidence for Dual Mechanism Controlled by the Promoter

Earth-Abundant Mixed-Metal Catalysts for Hydrocarbon Oxygenation

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Homo- and heterometallic polynuclear transition metal catalysts for alkane C H bonds oxidative functionalization: Recent advances

Cited by 120 publications

References 158 publications

Selective oxidation of cumene into 2-phenyl-2-propanol and acetophenone over activated carbon supported Co1.5PW12O40 material

Selective oxidation of cumene into 2-phenyl-2-propanol and acetophenone over activated carbon supported Co1.5PW12O40 material

Heterometallic CoIIIZnII Schiff Base Catalyst for Mild Hydroxylation of C(sp3)–H Bonds of Unactivated Alkanes: Evidence for Dual Mechanism Controlled by the Promoter

Earth-Abundant Mixed-Metal Catalysts for Hydrocarbon Oxygenation

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Product

Resources

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Selective oxidation of cumene into 2-phenyl-2-propanol and acetophenone over activated carbon supported Co_1.5PW₁₂O₄₀ material

Selective oxidation of cumene into 2-phenyl-2-propanol and acetophenone over activated carbon supported Co_1.5PW₁₂O₄₀ material