A tetra-cationic tetrapyridinoporphyrazinato Iron(II) grafted onto sulfonated SBA-15 as a novel heterogeneous catalyst for the aerobic oxidation of C(sp3)-H bonds in alkanes

Zahedi, Saeedeh; Safaei, Elham

doi:10.1016/j.apsusc.2021.149379

Cited by 11 publications

(3 citation statements)

References 130 publications

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“…In contrast to natural binuclear copper monooxygenase or the “biomimetic” supramolecular catalytic systems, , this new strategy enables direct O 2 activation via a photocatalytic manifold, allowing the oxygenation conversion to proceed under an oxygen or even an air atmosphere without the addition of any active oxygen species . It avoids the problems of using those oxidants to generate toxic waste or the stability and difficulty of recycling using the natural enzyme catalyst.…”

Section: Resultsmentioning

confidence: 99%

Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp³)–H Bonds via Multiphoton Excitation

Huang

Deng

et al. 2023

J. Am. Chem. Soc.

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Nature's blueprint provides the fundamental principles for expanding the use of abundant metals in catalysis; however, mimicking both the structure and function of copper enzymes simultaneously in one artificial system for selective C−H bond oxidation faces marked challenges. Herein, we report a new approach to the assembly of artificial monooxygenases utilizing a binuclear Cu 2 S 2 Cl 2 cluster to duplicate the identical structure and catalysis of the Cu A enzyme. The designed monooxygenase Cu-Cl-bpyc facilitates well-defined redox potential that initially activated O 2 via photoinduced electron transfer, and generated an active chlorine radical via a ligand-to-metal charge transfer (LMCT) process from the consecutive excitation of the in situ formed copper(II) center. The chlorine radical abstracts a hydrogen atom selectively from C(sp 3 )−H bonds to generate the radical intermediate; meanwhile, the O 2•− species interacted with the mimic to form mixed-valence species, giving the desired oxidization products with inherent product selectivity of copper monooxygenases and recovering the catalyst directly. This enzymatic protocol exhibits excellent recyclability, good functional group tolerance, and broad substrate scope, including some biological and pharmacologically relevant targets. Mechanistic studies indicate that the C−H bond cleavage was the rate-determining step and the cuprous interactions were essential to stabilize the active oxygen species. The well-defined structural characters and the fine-modified catalytic properties open a new avenue to develop robust artificial enzymes with uniform and precise active sites and high catalytic performances.

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Section: Resultsmentioning

confidence: 99%

Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp³)–H Bonds via Multiphoton Excitation

Huang

Deng

et al. 2023

J. Am. Chem. Soc.

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“…The oxygenation of hydrocarbons to produce usable oxygenated molecules is the potential strategy for maximizing the use of fossil resources [ 1 , 2 , 3 , 4 ]. In the current industry, widely accessible hydrocarbons may be converted into several key industrial chemicals or fundamental industrial raw materials through the shortest transformation path because of oxidative functionalization, in which partly oxygenated products (alcohols, aldehydes, and ketones), acids, and peroxides are produced [ 5 , 6 , 7 , 8 , 9 ].…”

Section: Introductionmentioning

confidence: 99%

Efficient and Selective Oxygenation of Cycloalkanes and Alkyl Aromatics with Oxygen through Synergistic Catalysis of Bimetallic Active Centers in Two-Dimensional Metal-Organic Frameworks Based on Metalloporphyrins

Zhou

Jin

et al. 2023

Biomimetics

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Confined catalytic realms and synergistic catalysis sites were constructed using bimetallic active centers in two-dimensional metal-organic frameworks (MOFs) to achieve highly selective oxygenation of cycloalkanes and alkyl aromatics with oxygen towards partly oxygenated products. Every necessary characterization was carried out for all the two-dimensional MOFs. The selective oxygenation of cycloalkanes and alkyl aromatics with oxygen was accomplished with exceptional catalytic performance using two-dimensional MOF Co-TCPPNi as a catalyst. Employing Co-TCPPNi as a catalyst, both the conversion and selectivity were improved for all the hydrocarbons investigated. Less disordered autoxidation at mild conditions, inhibited free-radical diffusion by confined catalytic realms, and synergistic C–H bond oxygenation catalyzed by second metal center Ni employing oxygenation intermediate R–OOH as oxidant were the factors for the satisfying result of Co-TCPPNi as a catalyst. When homogeneous metalloporphyrin T(4-COOCH3)PPCo was replaced by Co-TCPPNi, the conversion in cyclohexane oxygenation was enhanced from 4.4% to 5.6%, and the selectivity of partly oxygenated products increased from 85.4% to 92.9%. The synergistic catalytic mechanisms were studied using EPR research, and a catalysis model was obtained for the oxygenation of C–H bonds with O2. This research offered a novel and essential reference for both the efficient and selective oxygenation of C–H bonds and other key chemical reactions involving free radicals.

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“…The selective oxidation of arylalkanes to desired oxygen-containing compounds is a valuable reaction in the chemical industry with the increasing demand for various functional molecules by modern society. A representative example is the selective oxidation of ethylbenzene to acetophenone, which is an important organic intermediate for various pharmaceuticals, perfumes and fine chemicals [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 ]. However, the available methods for ethylbenzene oxidation generally show some drawbacks, such as harsh reaction conditions (e.g., high temperature/pressure), environmental pollutions (e.g., hazardous oxidants and organic solvents) and low catalytic performances [ 9 , 10 , 11 , 12 ].…”

Section: Introductionmentioning

confidence: 99%

Cobalt Encapsulated in Nitrogen-Doped Graphite-like Shells as Efficient Catalyst for Selective Oxidation of Arylalkanes

Li,

Ali,

Zuhra

et al. 2023

Molecules

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Selective oxidation of ethylbenzene to acetophenne is an important process in both organic synthesis and fine chemicals diligence. The cobalt-based catalysts combined with nitrogen-doped carbon have received great attention in ethylbenzene (EB) oxidation. Here, a series of cobalt catalysts with metallic cobalt nanoparticles (NPs) encapsulated in nitrogen-doped graphite-like carbon shells (Co@NC) have been constructed through the one-pot pyrolysis method in the presence of different nitrogen-containing compounds (urea, dicyandiamide and melamine), and their catalytic performance in solvent-free oxidation of EB with tert-butyl hydrogen peroxide (TBHP) as an oxidant was investigated. Under optimized conditions, the UCo@NC (urea as nitrogen source) could afford 95.2% conversion of EB and 96.0% selectivity to acetophenone, and the substrate scalability was remarkable. Kinetics show that UCo@NC contributes to EB oxidation with an apparent activation energy of 32.3 kJ/mol. The synergistic effect between metallic cobalt NPs and nitrogen-doped graphite-like carbon layers was obviously observed and, especially, the graphitic N species plays a key role during the oxidation reaction. The structure–performance relationship illustrated that EB oxidation was a free radical reaction through 1-phenylethanol as an intermediate, and the possible reaction mechanistic has been proposed.

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A tetra-cationic tetrapyridinoporphyrazinato Iron(II) grafted onto sulfonated SBA-15 as a novel heterogeneous catalyst for the aerobic oxidation of C(sp3)-H bonds in alkanes

Cited by 11 publications

References 130 publications

Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp³)–H Bonds via Multiphoton Excitation

Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp³)–H Bonds via Multiphoton Excitation

Efficient and Selective Oxygenation of Cycloalkanes and Alkyl Aromatics with Oxygen through Synergistic Catalysis of Bimetallic Active Centers in Two-Dimensional Metal-Organic Frameworks Based on Metalloporphyrins

Cobalt Encapsulated in Nitrogen-Doped Graphite-like Shells as Efficient Catalyst for Selective Oxidation of Arylalkanes

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A tetra-cationic tetrapyridinoporphyrazinato Iron(II) grafted onto sulfonated SBA-15 as a novel heterogeneous catalyst for the aerobic oxidation of C(sp3)-H bonds in alkanes

Cited by 11 publications

References 130 publications

Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp3)–H Bonds via Multiphoton Excitation

Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp3)–H Bonds via Multiphoton Excitation

Efficient and Selective Oxygenation of Cycloalkanes and Alkyl Aromatics with Oxygen through Synergistic Catalysis of Bimetallic Active Centers in Two-Dimensional Metal-Organic Frameworks Based on Metalloporphyrins

Cobalt Encapsulated in Nitrogen-Doped Graphite-like Shells as Efficient Catalyst for Selective Oxidation of Arylalkanes

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Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp³)–H Bonds via Multiphoton Excitation

Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp³)–H Bonds via Multiphoton Excitation