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, Год журнала: 2024, Номер 63(24), С. 11102 - 11112

Опубликована: Июнь 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.

Язык: Английский

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Photoelectrocatalytic application of vanadylporphyrin complexes directly extracted from oil

Catalysis Today, Год журнала: 2024, Номер 441, С. 114855 - 114855

Опубликована: Май 29, 2024

Non-pure primary Vanadyl petroporphyrins extracted from oil, i.e., PVP(Oil), have been impregnated on SBA-15 or SiO2. For comparison, synthetic vanadyl octaethylporphine, VP(S), was also the same siliceous materials. The characterization result of unsupported porphyrins and catalysts, by FTIR DR-UV-vis, confirm successful incorporation corresponding porphyrins. Electrochemical photoelectrochemical properties these catalysts evaluated through Impedance Spectroscopy (EIS), Mott-Schottky (MS) voltammetry tests. According to results, porphyrin show better response, regardless support used (either SiO2 SBA15), than ones, VP(S). Additionally, this study reveals that PVP(Oil) can be as photoelectrocatalysts for methyl red (MR) degradation (a common organic dye), showing almost a complete using PVP(Oil)-SBA15 catalyst after 3 h. Interestingly, an increase more 25% in kinetic constant MR is shown comparison

Язык: Английский

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

Inorganic Chemistry, Год журнала: 2024, Номер 63(27), С. 12506 - 12515

Опубликована: Июнь 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.

Язык: Английский

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Oxidovanadium(IV) Porphyrin-Imidazole Complex-Catalyzed One-Pot, Three-Component Green Synthesis of Biologically Active Pyrano[2,3-d]pyrimidine and 4H-Chromene Heterocycles

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 12, 2025

A β-functionalized porphyrin ligand {H2TPP(Phen)}, has been synthesized and subsequently employed as a dibasic tetradentate in synthesizing its vanadyl complex 2-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)-5,10,15,20-tetraphenylporphyrinatooxido-vanadium(IV)[VIVOTPP(Phen)] (1). Comprehensive characterization of the {H2TPP(Phen)} vanadyl(IV) (1) was achieved through various analytical spectroscopic techniques, including NMR, ultraviolet-visible (UV-vis), EPR, MALDI-TOF mass spectrometry elemental analysis. Electrochemical studies indicated that free base tends to four successive reduction peaks two oxidation observed cyclic voltammetry. In contrast, metalated [VIVOTPP(Phen)] displayed reversible reductions peaks. The vanadyl(IV)-porphyrin further an efficient reusable catalyst environmentally friendly, one-pot, three-component synthesis biologically clinically relevant pyrano[2,3-d]pyrimidine (Ca-Ch, Da-Dg) 4H-chromene (Ga-Gj, Ha-Hj) heterocycles. Based on current literature regarding multicomponent reactions, distinct plausible mechanistic pathways are postulated for these transformations. detailed investigation, isolation intermediates stepwise reaction analysis, revealed type 1,3-dicarbonyl compound used is pivotal determining operative pathway reactions. catalytic protocol developed heterocycles presents several advantages over existing methodologies, use eco-friendly solvent (ethanol), high product yields (up 97%), shorter time scale (30 min), turnover frequency (TOF) values 14.7 min-1), excellent reusability five cycles.

Язык: 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, Год журнала: 2023, Номер 26(34)

Опубликована: Сен. 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.

Язык: 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, Год журнала: 2024, Номер 27(9)

Опубликована: Янв. 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.

Язык: Английский

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Synthesis and characterization of meso-substituted oxidovanadium (IV) porphyrins for the selective epoxidation of alkenes in the presence of bicarbonate-assisted H2O2

Polyhedron, Год журнала: 2024, Номер 261, С. 117108 - 117108

Опубликована: Июнь 16, 2024

Язык: Английский

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The synthesis of highly nonplanar oxidovanadium(IV) porphyrins as robust catalysts for oxidative bromination of phenols in aqueous medium

Journal of Porphyrins and Phthalocyanines, Год журнала: 2024, Номер 28(04), С. 225 - 235

Опубликована: Апрель 1, 2024

Two new complexes, oxidovanadium(IV) 2,3,5,10,12,13,15,20-octaphenyl-7,8,17,18-tetrabromoporphyrin V(IV)O(OPP)Br 4 (2), and 2,3,5,10,12,13,15,20-octaphenyl-7,8,17,18-tetrachloroporphyrin V(IV)O(OPP)Cl (3) starting from 2,3,5,10,12,13,15,20-octaphenylporphyrin V(IV)O(OPP) (1) have been prepared in good yields characterized by various spectroscopic techniques. The single-crystal DFT-optimized structures of these porphyrins showed a highly nonplanar saddle-shape conformation the porphyrin macrocycle. In cyclic voltammograms, first ring oxidation potential reduction (2) anodic shift as compared to (1), indicating electron-deficient nature both porphyrins. state vanadium synthesized complexes +4 was confirmed EPR spectroscopy, exhibited axially compressed [Formula: see text] configuration. These were utilized catalysts for oxidative bromination thymol other phenol derivatives with excellent conversion ([Formula: 99.9%), selectivity, high TOF value (86869 h[Formula: text].

Язык: Английский

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Vanadyl Salen Complex Anchored on Polymer: An Efficient Catalyst for Selective Oxidation of Sulfides to Sulfoxides

Journal of Inorganic and Organometallic Polymers and Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 28, 2024

Язык: Английский

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