Enhanced Catalytic Activity of Binuclear Oxidovanadium(IV) Bisbenzimidazole Linked Porphyrin Dimer for the Generation of Biologically Active 3,4-Dihydropyrimidinones and Their Corresponding Thiones

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(24), P. 11102 - 11112

Published: June 4, 2024

Binuclear vanadyl(IV) porphyrin (V2BP), where two vanadium(IV) macrocycles are linked through benzimidazole units at the β-positions, has been prepared and characterized with various techniques, such as UV–vis, Fourier transform-infrared, electron paramagnetic resonance, cyclic voltammetry, density functional transform calculations, mass spectrometry. V2BP exhibits a red shift (Δλmax = 10 nm) in Soret band compared unsubstituted parent meso-tetraphenylporphyrin (VP). The synthesized binuclear (V2BP) further studied catalyst to explore single-pot multicomponent Biginelli reaction producing biologically active 3,4-dihydropyrimidin-2-(1H)-one (DHPM)-based biomolecules corresponding thiones under solvent-free conditions its catalytic activity Several conditions, amount of catalyst, time, solvent, temperature, have optimized obtain maximum yield DHPMs or thiones. β-functionalized dimer manifests much higher conversion (84–95% yield) high TON (4454–5037) TOF (1113–1259 h–1) values for one-pot literature. exhibited excellent recyclability up cycles.

Language: Английский

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Silver Anniversary of the Renaissance in Metallocorrole Chemistry

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

The 1999 discovery of one-pot corrole synthesis opened the floodgates for research on these unique macrocyclic chelating agents. enormous impact this has been documented in numerous reviews describing advances synthetic chemistry corroles and selected applications which are key components. Our silver anniversary review focuses structures reactions all well characterized corrole-chelated d- p-block metal complexes, including discussions their electronic excited-state physics chemistry. Emphasis is placed structure trinegative N4 coordination core, stabilizes high-valent metals activates low-valent ones, and, importantly, profoundly influences ground- reactivity. story highlights properties that have made them molecular components choice a plethora applications. These include utility sensing gases anions, rescue vital biomolecules from oxidative damage, destruction cancerous cells, catalysis critical organic synthesis, as those involved clean energy processes such production hydrogen reduction oxygen. In our view, will continue to grow by leaps bounds, most especially areas human health renewable science technology.

Language: Английский

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Synthesis, Spectral, Redox, and Sensing Studies of β-Dicyanovinyl-Appended Corroles and Their Metal Complexes

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(20), P. 7738 - 7752

Published: May 5, 2023

A new family of β-dicyanovinyl (DCV)-appended corroles represented as MTPC(MN) (where M = 3H, Cu, Ag, and Co(PPh3) MN malononitrile TPC 5,10,15-triphenylcorrole) were synthesized starting from the free base mono β-formyl corrole, H3TPC(CHO), characterized along with their respective MTPC(CHO) MTPC complexes to spectroscopic electrochemical properties in nonaqueous media. Comparisons between two series demonstrate a pronounced substituent effect β-DCV group on physicochemical making derivatives substantially easier reduce more difficult oxidize than formyl or unsubstituted corroles. In addition, colorimetric spectral detection 11 different anions (X) form tetrabutylammonium salts (TBAX, X PF6-, OAc-, H2PO4-, CN-, HSO4-, NO3-, ClO4-, F-, Cl-, Br-, I-) also investigated Of anions, only CN- was found induce changes UV-vis 1H NMR spectra metallocorroles. This data revealed that CuTPC(MN) AgTPC(MN) act chemodosimeters for selective cyanide ion via nucleophilic attack at vinylic carbon DCV substituent, while (PPh3)CoTPC(MN) acts chemosensor sensing axial coordination cobalt metal center. low-limit ions observed 1.69 ppm 1.17 toluene.

Language: Английский

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Effect of para‐Substituents on meso‐Functionalized Oxidovanadium(IV) Porphyrins as Catalysts for Oxygen Atom Transfer Mediated Oxidation of Benzoin to Benzil under Mild Conditions

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(30)

Published: July 31, 2023

Abstract Systematic analysis of the effect para ‐substituents (H, Cl, Br and OMe) on meso ‐phenyl group in vanadyl ‐tetraphenylporphyrins ([V IV O(TPP)] (R=H, 1 ), [V O(TCPP)] (R=Cl, 2 [ V O(TBPP)] (R=Br, 3 ) O(TMPP)] (R=OMe, 4 )) their properties catalytic oxygen atom transfer (OAT) for oxidation benzoin to benzil using DMSO as well 30 % aqueous H O sacrificial source have been studied. Electrochemical theoretical (density functional theory) studies are good agreement with influence these substituents property complexes. Complex ( displayed best activity conversion (92 %) h >99 product selectivity when was used an source, whereas excellent (~100 noticed 18 95 a oxygen. Furthermore, among complexes, electron‐withdrawing nature chloro substituent at p ‐position significantly influences transfer. Experimental simulated EPR confirmed +4 vanadium The structure , by single crystal X‐ray diffraction method, domed shape, displacement V(IV) ion from mean porphyrin plane follows order: (0.458 Å) < (0.459 (0.479 Å). We observed that dimethyl sulfide much.

Language: Английский

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Synthesis, Structural and Redox Properties of Vanadyl β‐Cyanoporphyrin and its Utilization as Efficient Catalyst for Epoxidation of Olefins and Oxidative Bromination of Phenols

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(9)

Published: Jan. 22, 2024

Abstract 2‐Cyano‐5,10,15,20‐tetraphenylporphyrin [H 2 TPPCN] ( 1 ) having cyano group at one of β ‐pyrrolic positions using nucleophilic substitution reaction tetrabutylammonium cyanide (TBACN) on free‐base 2‐nitro‐5,10,15,20‐tetraphenylporphyrin, and its oxidovanadium(IV) complex [V IV OTPPCN] were synthesized in good yields. Both the porphyrins have been characterized by UV‐Vis spectroscopy, mass spectrometry, cyclic voltammetric techniques. Single crystal X‐Ray crystallography revealed quasi‐planar geometry for . Compounds exhibited a red shift (λ max =7–9 nm) Soret band relative to [MTPP], where M=2H, V O owing electron‐withdrawing effect ‐position. The first oxidation (ΔE 1/2 =110–140 mV) reduction potentials =220–260 are anodically shifted [MTPP] O. Porphyrin has utilized as catalyst two reactions: epoxidation olefins bromination phenols. phenol KBr/H /HClO 4 water resulted 100 % conversion with TOF value high 19.6 s −1 0.5 h. Using H /NaHCO 3 CH CN/H solvent mixture 60 °C, was carried out, highest rate turnover frequency 1.9 achieved case cyclohexene. Catalyst recovered successfully end up 5 cycles had thermal stability, indicating industrial viability applicability. Moreover, these cyano‐functionalized could be further generation molecular self‐assemblies, post‐functionalization porphyrin core various applications. current findings this work present insights facile approach synthesis ‐cyano functionalized shed light utility vanadyl an efficient olefin reactions.

Language: Английский

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Highly Efficient β‐Functionalized Oxidomolybdenum(V) Corroles for Catalytic Oxidative Bromination of Phenols at Room Temperature

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(34)

Published: Sept. 19, 2023

Abstract Two new β ‐functionalized oxidomolybdenum(V) corroles, oxido[3‐formyl‐5,10,15‐triphenylcorrolato]molybdenum(V) ( Mo‐1 ) and oxido[3‐dicyanovinyl‐5,10,15‐triphenylcorrolato]molybdenum(V) Mo‐2 were synthesized characterized by various spectroscopic techniques electrochemical studies. manifests splitted B bands due to x y polarizations highly red shifted longest Q the electron‐deficient nature of dicyanovinyl group. EPR data showed that these complexes exhibit an axial compression with d xy 1 configuration. DFT studies revealed HOMO LUMO orbitals are stabilized in relative . exhibits two successive reversible reductions oxidation potentials cyclic voltammetry. Surprisingly, three oxidations; one extra reduction could possibly be moiety. The catalytic activities for oxidative bromination phenols using H 2 O ‐KBr‐HClO 4 mixture water have been explored exhibited excellent activity at a very low catalyst loading 0.0030 0.0028 mol%, respectively. Both Mo(V) corroles manifest much higher conversion TOF (59801–71174 h −1 earlier reported meso (20781–61646 ). Hence, mimic vanadium bromoperoxidase (VBPO) act as functional models applications. These catalysts reused upto 3 cycles rate 82 % indicating their thermal chemical stabilities.

Language: Английский

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Synthesis, characterization, and spectroscopic analysis of binuclear tungsten(VI) complexes with peroxidase-like activity

Polyhedron, Journal Year: 2023, Volume and Issue: 245, P. 116657 - 116657

Published: Sept. 9, 2023

Language: Английский

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Facile Synthesis of β‐Brominated Manganese Porphyrins and their Catalytic Potentials for Haloperoxidases‐Like Activity

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(9)

Published: Jan. 3, 2024

Abstract A novel and sustainable approach has been developed for the synthesis of β ‐brominated Mn porphyrins, [Mn III (Br)(TPPBr 4 )] ( 2 ), 6 3 ) IV (Br) (TPPBr 8 by self catalytic haloperoxidase mimicking activity (Br)(TPP)] [bromo( meso ‐tetraphenylporphyrinato)manganese(III)] 1 in aqueous medium under different mild controlled reaction conditions. By precisely tweaking important parameters (e. g. H O 2, HClO KBr), these polybrominated porphyrin complexes have synthesized. This method is safer applicable milder conditions than conventional procedures ‐bromination porphyrins. These were characterized various spectroscopic techniques, including UV–Vis spectroscopy, elemental analysis, MALDI‐TOF mass spectrometry, cyclic voltammetry, DFT calculations single crystal X‐ray diffraction analysis. Bromination phenol derivatives via haloperoxidase‐catalyzed using manganese explored. Carrying out at room temperature presence as an oxidant KBr a brominating agent acidic condition results good to excellent yield brominated product(s). Extra stability compared other catalysts due trans ‐[Br−Mn −Br] structure possibly prevents interaction with which makes it less potential catalyst , . Suitable mechanism proposed bromination substrates after identifying intermediates spectrometry.

Language: Английский

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Synthesis of Vanadyl Complexes of N-Confused Porphyrins and Their Bromoperoxidase-like Catalytic Activity

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(27), P. 12506 - 12515

Published: June 24, 2024

Two new vanadyl complexes of N-confused porphyrins (NCPs), [VONCTPP] (V-1) and [VONCP(OMe)8] (V-2), have been synthesized for the first time investigated as a catalyst oxidative bromination reaction phenol its derivatives. This article further delineates crystal structures, photophysical, redox properties both complexes. Complexes V-1 V-2 exhibited significant red shift in their absorption spectra compared with respective free bases. The single-crystal structure revealed that complex is 2H tautomeric form, while EPR studies +4 oxidation state vanadium metal having an axial compression dxy1 configuration. Catalytic potential bromoperoxidases-like activity has explored NCP chemistry excellent TOF values (4.7–6.3 s–1 7.3–8.7 V-2) using KBr source bromine H2O2 green oxidant aqueous acidic medium at 298 K. Notably, catalysts show recyclability over five cycles. vanadyl-metalated NCPs exhibit stability air.

Language: Английский

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Advances in metallopolymers: Synthesis strategies, catalytic insights, and environmental remediation applications

Sustainable Chemistry and Pharmacy, Journal Year: 2024, Volume and Issue: 40, P. 101630 - 101630

Published: June 2, 2024

Language: Английский

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