Light-assisted cyclohexane oxidation catalysis by a manganese(III) porphyrin immobilized onto zinc hydroxide salt and zinc oxide obtained by zinc hydroxide salt hydrothermal decomposition

Westrup, Kátia C. M.; Silva, Renaldo M. da; Mantovani, Karen Mary; Bach, Larissa; Stival, João Felipe; Zamora, Patrício G.P.; Machado, Guilherme Sippel; Nakagaki, Shirley

doi:10.1016/j.apcata.2020.117708

Cited by 20 publications

(7 citation statements)

References 117 publications

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“…Co-OOH and [Porp. Co=O] ⊕ ) were detected in ESI-MS analyses, which is in agreement with the adduct patterns between metalloporphyrins and O 2 reported in the relevant literature [57,62,68]. This was also strong evidence for the speculated mechanism process in Scheme 4.…”

Section: Mechanism Studysupporting

confidence: 90%

Efficient Inhibition of Deep Conversion of Partial Oxidation Products in C-H Bonds’ Functionalization Utilizing O2 via Relay Catalysis of Dual Metalloporphyrins on Surface of Hybrid Silica Possessing Capacity for Product Exclusion

Zhang,

Feng,

et al. 2024

Biomimetics

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To inhibit the deep conversion of partial oxidation products (POX-products) in C-H bonds’ functionalization utilizing O2, 5-(4-(chloromethyl)phenyl)-10,15,20-tris(perfluorophenyl)porphyrin cobalt(II) and 5-(4-(chloromethyl)phenyl)-10,15,20-tris(perfluorophenyl)porphyrin copper(II) were immobilized on the surface of hybrid silica to conduct relay catalysis on the surface. Fluorocarbons with low polarity and heterogeneous catalysis were devised to decrease the convenient accessibility of polar POX-products to catalytic centers on the lower polar surface. Relay catalysis between Co and Cu was designed to utilize the oxidation intermediates alkyl hydroperoxides to transform more C-H bonds. Systematic characterizations were conducted to investigate the structure of catalytic materials and confirm their successful syntheses. Applied to C-H bond oxidation, not only deep conversion of POX-products was inhibited but also substrate conversion and POX-product selectivity were improved simultaneously. For cyclohexane oxidation, conversion was improved from 3.87% to 5.27% with selectivity from 84.8% to 92.3%, which was mainly attributed to the relay catalysis on the surface excluding products. The effects of the catalytic materials, product exclusion, relay catalysis, kinetic study, substrate scope, and reaction mechanism were also investigated. To our knowledge, a practical and novel strategy was presented to inhibit the deep conversion of POX-products and to achieve efficient and accurate oxidative functionalization of hydrocarbons. Also, a valuable protocol was provided to avoid over-reaction in other chemical transformations requiring high selectivity.

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Section: Mechanism Studysupporting

confidence: 90%

Efficient Inhibition of Deep Conversion of Partial Oxidation Products in C-H Bonds’ Functionalization Utilizing O2 via Relay Catalysis of Dual Metalloporphyrins on Surface of Hybrid Silica Possessing Capacity for Product Exclusion

Zhang,

Feng,

et al. 2024

Biomimetics

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“…Furthermore, M cyclohexanol :M cyclohexanone (molar ratio) was raised from 1:1 (Entry 11 in Table 2 ) to 1.1:1. The increase in M cyclohexanol :M cyclohexanone (molar ratio) is a strong indicator of the OH· rebounding mechanism and suppression on the chaotic free-radical spread [ 78 , 79 , 80 , 81 ], which is one of the initial goals of conducting C–H bond oxygenation in porous MOFs. Because of the confined catalytic realms of two-dimensional MOFs, chaotic free-radical transport was reduced, which was compatible with our initial goal in this study.…”

Section: Resultsmentioning

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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“…[10][11][12]. Aim to achieve epoxides with great yield and selectivity, oxidation of ole ns can be commonly mediated with transition metal complexes as catalyst in homogeneous and heterogeneous catalytic systems [13][14][15][16]. Metalloporphyrins are a well-known class of metal complexes which mimic the cytochrome P-450 enzyme in oxidation reactions of metabolic processes [17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Mn-porphyrins Anchored onto Magnetic Nanoparticles via Different Linker Length: A Comparative Study in Aerobic Oxidation of Olefins

Rayati¹,

Shokoohi²

2022

Preprint

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In this research, meso-tetrakis(4-carboxyphenyl)porphyrinatomanganese(III) acetate has been immobilized onto the modified silica-coated Fe3O4 nanoparticles with linkers with different chain lengths (short, Fe3O4@SiO2-MnTCPP (C-1), medium Fe3O4@SiO2-NH2-MnTCPP (C-2), and long length, Fe3O4@SiO2-NHCO-NH2-MnTCPP (C-3)). The catalysts were characterized by various analytical and spectroscopic methods, including FT-IR, UV-Vis, XRD, FE-SEM, TEM, TGA, and VSM. A comparative study based on the difference in chain length of the linker in the oxidation of olefins with molecular oxygen was performed. The novel linker (long-chain catalyst) was designed to improve the performance of the catalytic activity (complete conversion of the α-methyl styrene, 4-methyl styrene and 4-chloro styrene was achieved after 2 h). The new heterogenized catalyst (Fe3O4@SiO2-NHCO-NH2-MnTCPP) not only shows higher catalytic activity in the oxidation of different olefins, but also shows better reusability of the catalyst.

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Light-assisted cyclohexane oxidation catalysis by a manganese(III) porphyrin immobilized onto zinc hydroxide salt and zinc oxide obtained by zinc hydroxide salt hydrothermal decomposition

Cited by 20 publications

References 117 publications

Efficient Inhibition of Deep Conversion of Partial Oxidation Products in C-H Bonds’ Functionalization Utilizing O2 via Relay Catalysis of Dual Metalloporphyrins on Surface of Hybrid Silica Possessing Capacity for Product Exclusion

Efficient Inhibition of Deep Conversion of Partial Oxidation Products in C-H Bonds’ Functionalization Utilizing O2 via Relay Catalysis of Dual Metalloporphyrins on Surface of Hybrid Silica Possessing Capacity for Product Exclusion

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

Mn-porphyrins Anchored onto Magnetic Nanoparticles via Different Linker Length: A Comparative Study in Aerobic Oxidation of Olefins

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