RESUMO
Selenium-derived electrocatalysts have been well explored for electrocatalytic hydrogen evolution reactions to mimic hydrogenase-like activity; however, the stability of these synthetic mimics is yet to be enhanced. In this study, we report the synthesis and characterization of a series of 1,10-phenanthroline-cobalt(II) phenolate selenoether complexes using 1,10-phenanthroline and 6-nitro-1,10-phenanthroline-Co(II)-dichloride and substituted bis-selenophenolate ligands. The synthesized cobalt(II) phenolate selenoether complexes have been characterized by CHN analysis, mass spectrometry, single crystal XRD, and UV-visible absorption spectroscopy. These complexes show electrocatalytic proton reduction from acetic acid at an overpotential of 0.45-0.56 V vs. Fc+/Fc and surpass previously reported selenium and sulfur-containing electrocatalysts. Furthermore, gas analysis from control potential electrolysis confirms that the cobalt(II) selenoethers act as electrocatalysts to produce H2 with a faradaic efficiency of 43-83% and show a turnover number of 3.24-58.60 molcat-1. The hydrogen evolution reaction (HER) was probed using deuterated acetic acid, which demonstrates an inverse kinetic isotopic effect (KIE) and is consistent with the formation of metal hydride intermediates. Furthermore, control experiments (post-dip analysis and multiple CV studies) have been performed to support the catalysis being due to a homogeneous process. Acid titration using UV-visible spectroscopy reveals that protonation is the prior step for electrocatalysis and assists in the formation of a cobalt hydride intermediate, which upon reaction with a proton generates hydrogen gas.
Assuntos
Hidrogenase , Selênio , Prótons , Hidrogenase/química , Cobalto/química , Hidrogênio/químicaRESUMO
Chalcogen-bonding interactions have recently gained considerable attention in the field of synthetic chemistry, structure, and bonding. Here, three organo-spiroselenuranes, having a Se(IV) center with a strong intramolecular Se···N chalcogen-bonded interaction, have been isolated by the oxidation of the respective bis(2-benzamide) selenides derived from an 8-aminoquinoline ligand. Further, the synthesized spiroselenuranes, when assayed for their antioxidant activity, show disproportionation of hydrogen peroxide into H2O and O2 with first-order kinetics with respect to H2O2 for the first time by any organoselenium molecules as monitored by 1H NMR spectroscopy. Electron-donating 5-methylthio-benzamide ring-substituted spiroselenurane disproportionates hydrogen peroxide at a high rate of 15.6 ± 0.4 × 103 µM min-1 with a rate constant of 8.57 ± 0.50 × 10-3 s-1, whereas 5-methoxy and unsubstituted-benzamide spiroselenuranes catalyzed the disproportionation of H2O2 at rates of 7.9 ± 0.3 × 103 and 2.9 ± 0.3 × 103 µM min-1 with rate constants of 1.16 ± 0.02 × 10-3 and 0.325 ± 0.025 × 10-3 s-1, respectively. The evolved oxygen gas from the spiroselenurane-catalyzed disproportion of H2O2 has also been confirmed by a gas chromatograph-thermal conductivity detector (GCTCD) and a portable digital polarographic dissolved O2 probe. Additionally, the synthesized spiroselenuranes exhibit thiol peroxidase antioxidant activities for the reduction of H2O2 by a benzenethiol co-reductant monitored by UV-visible spectroscopy. Next, the Se···N bonded spiroselenuranes have been explored as catalysts in synthetic oxidation iodolactonization and bromination of arenes. The synthesized spiroselenurane has activated I2 toward the iodolactonization of alkenoic acids under base-free conditions. Similarly, efficient chemo- and regioselective monobromination of various arenes with NBS catalyzed by chalcogen-bonded synthesized spiroselenuranes has been achieved. Mechanistic insight into the spiroselenuranes in oxidation reactions has been gained by 77Se NMR, mass spectrometry, UV-visible spectroscopy, single-crystal X-ray structure, and theoretical (DFT, NBO, and AIM) studies. It seems that the highly electrophilic nature of the selenium center is attributed to the presence of an intramolecular Se···N interaction and a vacant coordination site in spiroselenuranes is crucial for the activation of H2O2, I2, and NBS. The reaction of H2O2, I2, and NBS with tetravalent spiroselenurane would lead to an octahedral-Se(VI) intermediate, which is reduced back to Se(IV) due to thermodynamic instability of selenium in its highest oxidation state and the presence of a strong intramolecular N-donor atom.
Assuntos
Peróxido de Hidrogênio , Selênio , Antioxidantes/química , Benzamidas , Catálise , Peróxido de Hidrogênio/química , Oxirredução , Selênio/químicaRESUMO
6-(Ethylthio)-, 6-(ethylseleno)-, and 6-(ethyltelluro)-2,2,4-trimethyl-1,2-dihydroquinoline-three heavier chalcogen analogues of ethoxyquin-were prepared by dilithiation of the corresponding 6-bromodihydroquinoline followed either by treatment with the corresponding diethyl dichalcogenide (sulfur derivative) or by insertion of selenium/tellurium into the carbon-lithium bond, oxidation to a diaryl dichalcogenide, borohydride reduction, and finally alkylation of the resulting areneselenolate/arenetellurolate. Ethoxyquin, its heavier chalcogen analogues, and the corresponding 6-PhS, 6-PhSe, and 6-PhTe derivatives were assayed for both their chain-breaking antioxidative capacity and their ability to catalyze reduction of hydrogen peroxide in the presence of a stoichiometric amount of a thiol reducing agent (thiol peroxidase activity). Ethoxyquin itself turned out to be the best inhibitor of azo-initiated peroxidation of linoleic acid in a water/chlorobenzene two-phase system. In the absence of N-acetylcysteine as a coantioxidant in the aqueous phase, it inhibited peroxidation as efficiently as alpha-tocopherol but with a more than 2-fold longer inhibition time. In the presence of 0.25 mM coantioxidant in the aqueous phase, the inhibition time was further increased by almost a factor of 2. This is probably due to thiol-mediated regeneration of the active antioxidant across the lipid-aqueous interphase. The ethyltelluro analogue 1d of ethoxyquin was a similarly efficient quencher of peroxyl radicals compared to the parent in the two-phase system, but less regenerable. Ethoxyquin was found to inhibit azo-initiated oxidation of styrene in the homogeneous phase (chlorobenzene) almost as efficiently (kinh = (2.0 +/- 0.2) x 106 M-1 s-1) as alpha-tocopherol with a stoichiometric factor n = 2.2 +/- 0.1. At the end of the inhibition period, autoxidation was additionally retarded, probably by ethoxyquin nitroxide formed during the course of peroxidation. The N-H bond dissociation enthalpy of ethoxyquin (81.3 +/- 0.3 kcal/mol) was determined by a radical equilibration method using 2,6-dimethoxyphenol and 2,6-di-tert-butyl-4-methylphenol as equilibration partners. Among the investigated compounds, only the tellurium analogues 1d and, less efficiently, 1g had a capacity to catalyze reduction of hydrogen peroxide in the presence of thiophenol. Therefore, analogue 1d is the only antioxidant which is multifunctional (chain-breaking and preventive) in character and which can act in a truly catalytic fashion to decompose both peroxyl radicals and organic hydroperoxides in the presence of suitable thiol reducing agents.
Assuntos
Antioxidantes/química , Química Orgânica/métodos , Etoxiquina/química , Selênio/química , Enxofre/química , Telúrio/química , Catálise , Clorobenzenos/química , Espectroscopia de Ressonância de Spin Eletrônica , Cinética , Ácido Linoleico/química , Modelos Químicos , Substâncias Redutoras/farmacologia , Fatores de Tempo , Água/químicaRESUMO
Diaryl chalcogenide synthesis employing diaryl dichalcogenides and aryl halides as starting materials in the presence of excess magnesium and a catalytic amount of CuI/bipyridyl is significantly improved by microwave heating. Reaction times can be reduced from 2 to 3 days to 6-8 h. Both aryl bromides and aryl chlorides can be used as substrates in the substitution reaction. The procedure is useful not only for diaryl sulfide and diaryl selenide synthesis but also for the preparation of unsymmetrical diaryl tellurides. Starting from suitable aryl halides, the novel microwave-assisted procedure was used for the facile preparation of novel chalcogen analogues (PhS-, PhSe-, and PhTe-) of various antioxidants (ethoxyquin and 3-pyridinol). Attempts to use dialkyl dichalcogenides for the coupling of alkylchalcogeno moieties to aryl halides were only successful in the case of long-chain (such as n-octyl) disulfides and diselenides.