696-71-9Relevant academic research and scientific papers
Catalytic oxyfunctionalization of saturated hydrocarbons by non-heme oxo-bridged diiron(III) complexes: role of acetic acid on oxidation reaction
Agarwalla, Uday Sankar
, p. 583 - 588 (2020)
Oxo-bridged diiron(III) complexes [Fe2O(L1)2(H2O)2](ClO4)4 (1) and [Fe2O(L2)2(H2O)2](ClO4)4 (2), where L1 and L2 are tetradentate N-donor N,N′-bis(2-pyridylmethyl)-1,2-cyclohexanediamine and N,N′-bis(2-pyridylmethyl)ethane-1,2-diamine respectively, have been isolated as synthetic models of non-heme iron oxygenases and characterized by physicochemical and spectroscopic methods. Both the complexes have been studied as catalysts for the oxyfunctionalization of saturated hydrocarbons using green hydrogen peroxide (H2O2) as oxidant under mild conditions. The selectivity (A/K) and regioselectivity (3°/2°) in oxidative C–H functionalization of alkanes suggests the involvement of metal-based intermediate in the oxygenation reaction. The catalytic efficiency is found to be strongly dependent on the presence of acetic acid. Remarkable increase in conversion and selectivity favoring the formation of alcohols in the oxidation of cyclohexane and cyclooctane and exclusive hydroxylation of adamantane with drastic enhancement of regioselectivity has been achieved by the addition of acetic acid in the presence of H2O2.
Efficient and selective oxidation of hydrocarbons with tert-butyl hydroperoxide catalyzed by oxidovanadium(IV) unsymmetrical Schiff base complex supported on γ-Fe2O3 magnetic nanoparticles
Samani, Mahnaz,Ardakani, Mehdi Hatefi,Sabet, Mohammad
, p. 1481 - 1494 (2022/01/22)
The catalytic activity of an oxidovanadium(IV) unsymmetrical Schiff base complex supported on γ-Fe2O3 magnetic nanoparticles, γ-Fe2O3@[VO(salenac-OH)] in which salenac-OH = [9-(2′,4′-dihydroxyphenyl)-5,8-diaza-4
Pyridazine N-Oxides as Photoactivatable Surrogates for Reactive Oxygen Species
Basistyi, Vitalii S.,Frederich, James H.
supporting information, p. 1907 - 1912 (2022/03/27)
A method for the photoinduced evolution of atomic oxygen from pyridazine N-oxides was developed. This underexplored oxygen allotrope mediates arene C-H oxidation within complex, polyfunctional molecules. A water-soluble pyridazine N-oxide was also developed and shown to promote photoinduced DNA cleavage in aqueous solution. Taken together, these studies highlight the utility of pyridazine N-oxides as photoactivatable O(3P) precursors for applications in organic synthesis and chemical biology.
Synthesis of new rhodium(III) complex by benzylic C[sbnd]S bond cleavage of thioether containing NNS donor Schiff base ligand: Investigation of catalytic activity towards transfer hydrogenation of ketones
Biswas, Sujan,Das, Akash,Kumar Manna, Chandan,Kumar Mondal, Tapan,Naskar, Rahul
, (2020/11/04)
A new rhodium(III)-triphenylphosphine mixed ligand complex, [Rh(PPh3)(L)Cl2] (1) is synthesized by benzylic C[sbnd]S bond cleavage of L-CH2Ph ligand (where, L-CH2Ph = 2-(benzylthio)-N-(pyridin-2-ylmethylene)aniline). The complex is thoroughly characterized by several spectroscopic techniques. Geometry of the complex is confirmed by single crystal X-ray crystallography. Electronic structure, redox properties, absorption and emission properties of the complex were studied. DFT and TDDFT calculations were carried out to interpret the electronic structure and absorption properties of the complex respectively. The synthesized Rh(III) complex was tested as catalyst towards transfer hydrogenation reaction of ketones in iPrOH and an excellent catalytic conversion was observed under mild conditions.
Time-Dependent Self-Assembly of Copper(II) Coordination Polymers and Tetranuclear Rings: Catalysts for Oxidative Functionalization of Saturated Hydrocarbons
Costa, Ines F. M.,Kirillova, Marina V.,André, Vania,Fernandes, Tiago A.,Kirillov, Alexander M.
supporting information, p. 14491 - 14503 (2021/07/19)
This study describes a time-dependent self-assembly generation of new copper(II) coordination compounds from an aqueous-medium reaction mixture composed of copper(II) nitrate, H3bes biobuffer (N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid), ammonium hydroxide, and benzenecarboxylic acid, namely, 4-methoxybenzoic (Hfmba) or 4-chlorobenzoic (Hfcba) acid. Two products were isolated from each reaction, namely, 1D coordination polymers [Cu3(μ3-OH)2(μ-fmba)2(fmba)2(H2O)2]n (1) or [Cu2(μ-OH)2(μ-fcba)2]n (2) and discrete tetracopper(II) rings [Cu4(μ-Hbes)3(μ-H2bes)(μ-fmba)]·2H2O (3) or [Cu4(μ-Hbes)3(μ-H2bes)(μ-fcba)]·4H2O (4), respectively. These four compounds were obtained as microcrystalline air-stable solids and characterized by standard methods, including the single-crystal X-ray diffraction. The structures of 1 and 2 feature distinct types of metal-organic chains driven by the μ3- or μ-OH- ligands along with the μ-benzenecarboxylate linkers. The structures of 3 and 4 disclose the chairlike Cu4 rings assembled from four μ-bridging and chelating aminoalcoholate ligands along with μ-benzenecarboxylate moieties playing a core-stabilizing role. Catalytic activity of 1-4 was investigated in two model reactions, namely, (a) the mild oxidation of saturated hydrocarbons with hydrogen peroxide to form alcohols and ketones and (b) the mild carboxylation of alkanes with carbon monoxide, water, and peroxodisulfate to generate carboxylic acids. Cyclohexane and propane were used as model cyclic and gaseous alkanes, while the substrate scope also included cyclopentane, cycloheptane, and cyclooctane. Different reaction parameters were investigated, including an effect of the acid cocatalyst and various selectivity parameters. The obtained total product yields (up to 34% based on C3H8 or up to 47% based on C6H12) in the carboxylation of propane and cyclohexane are remarkable taking into account an inertness of these saturated hydrocarbons and low reaction temperatures (50-60 °C). Apart from notable catalytic activity, this study showcases a novel time-dependent synthetic strategy for the self-assembly of two different Cu(II) compounds from the same reaction mixture.
Mild oxidative functionalization of cycloalkanes catalyzed by novel dicopper(II) cores
Trusau, Kiryl I.,Kirillova, Marina V.,André, Vania,Usevich, Andrew I.,Kirillov, Alexander M.
, (2021/02/09)
The search for new transition metal based catalytic systems that are active in the oxidative functionalization of such inert substrates as saturated hydrocarbons continues to be an important research direction in molecular catalysis. In the present study, two new copper(II) coordination compounds, namely a discrete dimer [Cu2(μ-H2tea)2(nfa)2]·2H2O (1) and a 1D coordination polymer [Cu2(μ-H2tea)2(μ-Htma)]n·4nH2O (2) were synthesized and applied as homogeneous catalysts for the mild oxidative functionalization of cycloalkanes (cyclopentane, cyclohexane, cycloheptane, and cyclooctane). Both products 1 and 2 were self-assembled in aqueous medium from copper(II) nitrate, triethanolamine (H3tea), sodium hydroxide, and 2-naphthoic (Hnfa) or trimesic (H3tma) acids, isolated as stable crystalline solids, and fully characterized by standard methods including single-crystal X-ray diffraction. Their structures feature a similar type of dicopper(II) triethanolaminate cores that are decorated by terminal or bridging aromatic carboxylate ligands. Two model catalytic reactions were investigated, namely the oxidation of cycloalkanes by H2O2 to produce cycloalkyl hydroperoxides as intermediate products and then a mixture of cyclic alcohols and ketones as final products, and the carboxylation of cycloalkanes with CO/S2O82?/H2O to form cycloalkanecarboxylic acids as main products. These model reactions undergo under very mild conditions (50?60 °C) and show good efficiency. Substrate scope, selectivity features, and the effects of reaction parameters were investigated and discussed in detail. This study widens the family of multicopper(II) cores capable of catalyzing the oxidative functionalization of saturated hydrocarbons under mild conditions.
Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn(AcO)2: A practical strategy to inhibit the formation of aliphatic diacids
Shen, Hai-Min,Wang, Xiong,Ning, Lei,Guo, A-Bing,Deng, Jin-Hui,She, Yuan-Bin
, (2020/11/20)
The direct sources of aliphatic acids in cycloalkanes oxidation were investigated, and a strategy to suppress the formation of aliphatic acids was adopted through enhancing the catalytic transformation of oxidation intermediates cycloalkyl hydroperoxides to cycloalkanols by Zn(II) and delaying the emergence of cycloalkanones. Benefitted from the delayed formation of cycloalkanones and suppressed non-selective thermal decomposition of cycloalkyl hydroperoxides, the conversion of cycloalkanes and selectivity towards cycloalkanols and cycloalkanones were increased simultaneously with satisfying tolerance to both of metalloporphyrins and substrates. For cyclohexane, the selectivity towards KA-oil was increased from 80.1% to 96.9% meanwhile the conversion was increased from 3.83 % to 6.53 %, a very competitive conversion level with higher selectivity compared with current industrial process. This protocol is not only a valuable strategy to overcome the problems of low conversion and low selectivity lying in front of current cyclohexane oxidation in industry, but also an important reference to other alkanes oxidation.
Three metal centers (Co _AOMARKENCODEAMPX0AOA) Cu _AOMARKENCODEAMPX0AOA Method using Zn) 2D MOFs/ultraviolet light to catalyze oxidation of cycloalkane
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Paragraph 0028; 0079-0080, (2021/11/06)
The invention relates to a three-metal center (Co _AOMARKENCODEAMPX0AOA). Cu _AOMARKENCODEAMPX0AOA The method comprises Zn) 2D MOFs/ultraviolet light catalytic oxidation of cycloalkane to synthesize cycloalkyl alcohol and cycloalkanone, and belongs to the field of industrial catalysis and fine organic synthesis. To the application method, metalloporphyrin three-metal center (Co _AOMARKENCODEAMPX0AOA) is used. Cu _AOMARKENCODEAMPX0AOA Zn) 2D MOFs dispersed in cycloalkane, wherein metalloporphyrin three-metal center (Co _AOMARKENCODEAMPX0AOA) Cu _AOMARKENCODEAMPX0AOA Zn) 2D MOFs mass is 0.01% - 20%, g / mol of the substance of the cycloalkane, and the reaction system is sealed. An oxidant is introduced, the ultraviolet lamp is a light source, and the reaction liquid of the stirring reaction 2.0-24 . 0h. is subjected to post-treatment to obtain the product cycloalkyl alcohol and cycloalkyl ketone. The method provided by the invention has the advantages of low reaction temperature, mild reaction conditions, high reaction efficiency, high selectivity of cycloalkyl alcohol and cycloalkyl ketone, less byproducts and small environmental impact. The invention provides a high efficiency. Available, safe cycloalkanes selectively catalyze the oxidative synthesis of cycloalkyl alcohols and cycloalkyl ketones.
Pincerlike molybdenum complex and preparation method thereof, catalytic composition and application thereof, and alcohol preparation method
-
Paragraph 0134-0140, (2021/08/11)
The invention discloses a clamp-type molybdenum complex, a preparation method, a corresponding catalyst composition and application. The method comprises the steps: obtaining 9 molybdenum complexes with different structures through coordination reaction of 2-(substituent ethyl)-(5, 6, 7, 8-tetrahydroquinolyl) amine and a corresponding carbonyl molybdenum metal precursor; and catalyzing a ketone compound transfer hydrogenation reaction through a molybdenum complex to generate 40 alcohol compounds. The preparation method of the molybdenum complex is simple, high in yield and good in stability. For a transfer hydrogenation reaction of ketone, the molybdenum-based catalytic system has high catalytic activity and small molybdenum loading capacity, is used for production of aromatic and aliphatic alcohols, and has the advantages of simple method, small environmental pollution and high yield.
Hydroxylation of Unactivated C(sp3)-H Bonds with m-Chloroperbenzoic Acid Catalyzed by an Iron(III) Complex Supported by a Trianionic Planar Tetradentate Ligand
Morimoto, Yuma,Hanada, Shinichi,Kamada, Ryusuke,Fukatsu, Arisa,Sugimoto, Hideki,Itoh, Shinobu
supporting information, p. 7641 - 7649 (2021/02/03)
Hydroxylation of cyclohexane with m-chloroperbenzoic acid was examined in the presence of an iron(III) complex supported by a trianionic planar tetradentate ligand. The present reaction system shows a high turnover number of 2750 with a high product selectivity of alcohol (93%). The turnover frequency was 0.51 s-1, and the second-order rate constant (k) for the C-H bond activation of cyclohexane was 1.08 M-1 s-1, which is one of the highest values among the iron complexes in the oxidation of cyclohexane so far reported. The present catalytic system can be adapted to the hydroxylation of substrates having only primary C-H bonds such as 2,2,3,3-tetramethylbutane as well as gaseous alkanes such as butane, propane, and ethane. The involvement of an iron(III) acyl peroxido complex as the reactive species was suggested by spectroscopic measurements of the reaction solution.
