Efficient and selective oxidation of alcohols with tert-BuOOH catalyzed by a dioxomolybdenum(VI) Schiff base complex under organic solvent-free conditions

Ardakani, Mehdi Hatefi; Saeednia, Samira; Parizi, Zahra Pakdin; Rafeezadeh, Mahdieh

doi:10.1007/s11164-016-2531-x

Cited by 19 publications

(10 citation statements)

References 32 publications

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“…These results concerning the existence of a radical mechanism were the first to the best of our knowledge as we could not find evidence in the literature for similar findings in related systems [23][24][25]. However, proof of evidence for ruling in or ruling out radical mechanisms was also not found.…”

Section: Mechanistic Studycontrasting

confidence: 71%

“…The catalytic performance demonstrated by the two different catalysts was relevant and their performances in the oxidation of BzOH to BzCHO using TBHP or H2O2 with or without solvent are compared in Table 4. As shown in entries 14-16, the overall catalytic performance of the MoO2-Fe2O3 and MoO2 calcined nanomaterials was comparable or better than other catalytic nanomaterials reported in the literature [6,[23][24][25][26][27][28][29][30][31][32][33][34]. The catalysts shown in Table 4 cover a wide selection of The catalytic performance demonstrated by the two different catalysts was relevant and their performances in the oxidation of BzOH to BzCHO using TBHP or H 2 O 2 with or without solvent are compared in Table 4.…”

Section: Mechanistic Studymentioning

confidence: 71%

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Selective Catalytic Oxidation of Benzyl Alcohol by MoO2 Nanoparticles

Gaspar

Nunes

2020

Catalysts

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Selective oxidation of benzyl alcohol to benzaldehyde was carried out with MoO2 nanoparticles (MoO2 NPs). MoO2 NPs were synthesized by two different approaches and characterized by several techniques. The synthesis was done by a hydrothermal procedure using ethylenediamine and either Fe2O3 or hydroquinone. In the latter case, an additional calcination step under N2 was performed to eliminate passivating agents at the surface of the nanoparticles. The synthesized nanocatalysts showed similar catalytic properties, being efficient catalysts in the oxidation of benzyl alcohol. High substrate conversion and product selectivity were achieved under all tested conditions. Studies were conducted using two different oxidants: tert-butyl hydroperoxide and hydrogen peroxide, in our continuous effort to obtain more efficient catalysts for more sustainable catalytic processes. When H2O2 was used as the oxidant, 94% yield was achieved with 100% selectivity for benzaldehyde, which was a very promising result to undergo other studies with this system. Moreover, to elucidate some aspects of the reaction mechanism, a study was conducted, and it was possible to conclude that the reaction undergoes, to some extent, through a radical mechanism with both oxidants.

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Section: Mechanistic Studycontrasting

confidence: 71%

Section: Mechanistic Studymentioning

confidence: 71%

Selective Catalytic Oxidation of Benzyl Alcohol by MoO2 Nanoparticles

Gaspar

Nunes

2020

Catalysts

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“…Aldehydes and ketones are essential products and intermediates in the fine chemical redox processes of alcohols. Moreover, most of recent research highlights on the chemoselectivity of the alcohols oxidation to their corresponding aldehydes and ketones by different pre‐catalyst of transition metal complexes . Catalytic oxidation of sulfides has been progressed recently using different oxidants .…”

Section: Resultsmentioning

confidence: 99%

Catalytic activity of nickel(II), copper(II) and oxovanadium(II)‐dihydroindolone complexes towards homogeneous oxidation reactions

Adam

2018

Applied Organom Chemis

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Three novel paramagnetic metal complexes (MH 2 ID) of Ni 2+ , Cu 2+ and VO 2+ ions with 3-hydroxy-3,3'-biindoline-2,2'-dione (dihydroindolone, H 4 ID) were synthesized and characterized by different spectroscopic methods. The ligand (H 4 ID) was synthesized via homocoupling reaction of isatin in presence of phenylalanine in methanol. Complexation of low valent Ni 2+ , Cu 2+ ions and high valent VO 2+ ions with H 4 ID carried out in 1: 2 molar ratios. A comparison in the catalytic potential of paramagnetic complexes of low and high valent metal ion was explored in the oxidation processes of cis-cyclooctene, benzyl alcohol and thiophene by an aqueous H 2 O 2 , as a green terminal oxidant, in the presence and absence of acetonitrile, as an organic solvent, at 85°C. NiH 2 ID, CuH 2 ID and VOH 2 ID show good catalytic activity, i.e. good chemoand regioselectivity. VOH 2 ID has the highest catalytic potential compared to both Ni 2+and Cu 2+ -species in the same homogenous aerobic atmosphere.Catalytic oxidation of other alkenes and alcohols was also studied using NiH 2 ID, CuH 2 ID or VOH 2 ID as a pre-catalyst by an aqueous H 2 O 2 . A mechanistic pathway for those oxidation processes was proposed.

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“…[69] Based on the literature, the oxygen transfer process could be progressed in the presence of a coordinated solvent molecule in the catalyst, [37] in which the oxidant molecule may replace the solvent molecule (water or methanol, ROH) and then bond to the central metal ion (A) in order to generate an active oxo−/peroxomolybdenum complex intermediates, [70] [58] as tBuOO − anion to the Lewis acidic Mo VI ion. [42,71] The bonded tBuOO − to Mo VI ion caused migration of H + of the oxidant to the cis-terminal oxygen of Mo = O species giving peroxointermediate C (in Scheme 3). This was studied previously with new cyclopentadienyl molybdenum imidazo[1,5-a]pyridine-3-ylidene complexes in the olefin epoxidation using tBuOOH.…”

Section: Catalytic (Ep)oxidation Studiesmentioning

confidence: 99%

Bis‐dioxomolybdenum (VI) oxalyldihydrazone complexes: Synthesis, characterization, DFT studies, catalytic epoxidation potential, molecular modeling and biological evaluations

Adam

Ahmed

Elhady

et al. 2020

Applied Organom Chemis

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Two cis‐bis‐dioxomolybdenum oxalylsalicylidenedihydrazone complexes (MoO2L1 and MoO2L2) were synthesized via the complexation of dioxomolybdenum (VI) acetylacetonate with oxalylsalicylidenedihydrazone (H2L1) and p‐sodium sulfonate oxalylsalicylidenedihydrazone (H2L2) bis‐Schiff base chelating ligands, respectively. The structures of the newly synthesized complexes were confirmed by 1H‐ and 13C‐NMR, IR, ultraviolet–visible and mass spectra, as well as elemental analyses (EA) and conductivity measurements. The spectrophotometric continuous variation method revealed the formation of 2: 1 (metal: ligand molar ratios). DFT studies were applied for the ligands and their Mo‐chelates. Interestingly, the bis‐MoO2(VI) oxalyldihydrazone complexes showed remarkable catalytic sufficiency towards the selective (ep)oxidation of 1,2‐cyclooctene, benzyl alcohol and thiophene using H2O2 or tert‐butyl hydroperoxide (tBuOOH) at 85 °C. Under aqueous conditions, the MoO2L2 (with p‐sodium sulfonate substituent) exhibited superior that of the MoO2L1 (without p‐NaSO3―group), highlighting the role of sodium sulfonate substituent in the catalytic progress of the Mo‐chelate. The ligands (H2L1 and H2L2) and their corresponding Mo‐complexes (MoO2L1 and MoO2L2) were assessed for their antitumor and antimicrobial activities. Furthermore, the antioxidant activity was also evaluated using the 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) and superoxide dismutase (SOD) assays. The binding nature between the Mo‐complexes and calf thymus DNA (ctDNA) was also studied within spectroscopic and hydrodynamic techniques.

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Efficient and selective oxidation of alcohols with tert-BuOOH catalyzed by a dioxomolybdenum(VI) Schiff base complex under organic solvent-free conditions

Cited by 19 publications

References 32 publications

Selective Catalytic Oxidation of Benzyl Alcohol by MoO2 Nanoparticles

Selective Catalytic Oxidation of Benzyl Alcohol by MoO2 Nanoparticles

Catalytic activity of nickel(II), copper(II) and oxovanadium(II)‐dihydroindolone complexes towards homogeneous oxidation reactions

Bis‐dioxomolybdenum (VI) oxalyldihydrazone complexes: Synthesis, characterization, DFT studies, catalytic epoxidation potential, molecular modeling and biological evaluations

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