Polyfunctional Sterically Hindered Catechols with Additional Phenolic Group and Their Triphenylantimony(V) Catecholates: Synthesis, Structure, and Redox Properties

Smolyaninov, I. V.; Poddel’sky, Andrey I.; Smolyaninova, S. A.; Arsenyev, Maxim V.; Fukin, Georgy K.; Берберова, Н. Т.

doi:10.3390/molecules25081770

Cited by 13 publications

(5 citation statements)

References 92 publications

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“…The lengths of the oxygen-carbon bonds O(1)–C(1) and O(2)–C(2) as well as the carbon-carbon of the C(1–6) ring are characteristic of catechols [ 25 , 65 , 66 , 67 , 68 ]: O(1)–C(1), 1.377(2) Å; O(2)–C(2), 1.362(2) Å. The carbon-carbon bonds of the six-membered carbon ring C(1–6) average 1.395 ± 0.015 Å and ones are aromatic.…”

Section: Resultsmentioning

confidence: 99%

“…The formed precipitate of pyridinium salt was filtered off, dried in a vacuum. Compound 3 was previously prepared [ 25 ].…”

Section: Methodsmentioning

confidence: 99%

“…Along with the pronounced biological activity, these compounds are widely used to obtain functionalized materials [ 13 , 14 , 15 , 16 ]; they serve as building blocks for coatings design [ 17 ], as the basis for organic batteries and redox capacitors [ 18 , 19 ], and as redox-based molecular memory-films [ 20 ] due to their ability to accept, store and donate electrons and protons. Researchers consider S-functionalized sterically hindered catechols (quinones) as promising chelating ligands in metal complexes [ 21 , 22 , 23 , 24 , 25 , 26 , 27 ], polynuclear compounds and coordination polymers [ 28 , 29 ].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Antioxidant Activity of New Catechol Thioethers with the Methylene Linker

et al. 2022

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Novel catechol thio-ethers with different heterocyclic substituents at sulfur atom were prepared by reacting 3,5-di-tert-butyl-6-methoxymethylcatechol with functionalized thiols under acidic conditions. A common feature of compounds is a methylene bridge between the catechol ring and thioether group. Two catechols with the thio-ether group, bound directly to the catechol ring, were also considered to assess the effect of the methylene linker on the antioxidant properties. The crystal structures of thio-ethers with benzo-thiazole moieties were established by single-crystal X-ray analysis. The radical scavenging and antioxidant activities were determined using 2,2′-diphenyl-1-picrylhydrazyl radical test, ABTS∙+, CUPRAC (TEAC) assays, the reaction with superoxide radical anion generated by xanthine oxidase (NBT assay), the oxidative damage of the DNA, and the process of lipid peroxidation of rat liver (Wistar) homogenates in vitro. Most catechol-thioethers exhibit the antioxidant effect, which varies from mild to moderate depending on the model system. The dual anti/prooxidant activity characterizes compounds with adamantyl or thio-phenol substituent at the sulfur atom. Catechol thio-ethers containing heterocyclic groups (thiazole, thiazoline, benzo-thiazole, benzo-xazole) can be considered effective antioxidants with cytoprotective properties. These compounds can protect molecules of DNA and lipids from the different radical species.

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Section: Resultsmentioning

confidence: 99%

“…The formed precipitate of pyridinium salt was filtered off, dried in a vacuum. Compound 3 was previously prepared [ 25 ].…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis and Antioxidant Activity of New Catechol Thioethers with the Methylene Linker

et al. 2022

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“…In all structures, the redox active ligand is in catecholato form. The O–C bonds in molecules of 1 , 3 , 4 , 5 , 8 , and 10 lie in the range of 1.357–1.366 Ǻ typical for ordinary O–C bonds in antimony catecholates [ 64 , 65 , 66 , 67 , 68 , 69 , 70 ], the six-membered carbon cycles are aromatic with the average C–C distances of 1.400, 1.401, 1.402, 1.402, 1.405, and 1.407 Ǻ, respectively. The metrical oxidation state (MOS) for complexes was calculated according to S.N.…”

Section: Resultsmentioning

confidence: 99%

Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties

et al. 2022

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A series of binuclear triphenylantimony(V) bis-catecholato complexes 1–11 of the type (Cat)Ph3Sb-linker-SbPh3(Cat) was prepared by a reaction of the corresponding mononuclear catecholates (Cat)SbPh3 with a neutral bidentate donor linker ligands pyrazine (Pyr), 4,4′-dipyridyl (Bipy), bis-(pyridine-4-yl)-disulfide (PySSPy), and diazobicyclo[2,2,2]octane (DABCO) in a dry toluene: Cat = 3,6-di-tert-butyl-catecholate (3,6-DBCat), linker = Pyr (1); PySSPy (2); Bipy (3); DABCO (4); Cat = 3,5-di-tert-butyl-catecholate (3,5-DBCat), linker = Bipy (5); DABCO (9); Cat = 4,5-(piperazine-1,4-diyl)-3,6-di-tert-butylcatecholate (pip-3,6-DBCat), linker = Bipy (6); DABCO (10); Cat = 4,5-dichloro-3,6-di-tert-butylcatecholate (4,5-Cl2-3,6-DBCat), linker = Bipy (7); DABCO (11); and Cat = 4,5-dimethoxy-3,6-di-tert-butylcatecholate (4,5-(MeO)2-3,6-DBCat), linker = Bipy (8). The same reaction of (4,5-Cl2-3,6-DBCat)SbPh3 with DABCO in an open atmosphere results in a formation of 1D coordination polymer {[(4,5-Cl2-3,6-DBCat)SbPh3·H2O]·DABCO}n (12). Bis-catecholate complex Ph3Sb(Cat-Spiro-Cat)SbPh3 reacts with Bipy as 1:1 yielding a rare macrocyclic tetranuclear compound {Ph3Sb(Cat-Spiro-Cat)SbPh3∙(Bipy)}2 (13). The molecular structures of 1, 3, 4, 5, 8, 10, 12, and 13 in crystal state were established by single-crystal X-ray analysis. Complexes demonstrate different types of relative spatial positions of mononuclear moieties. The nature of chemical bonds, charges distribution, and the energy of Sb...N interaction were investigated in the example of complex 5. The electrochemical behavior of the complexes depends on the coordinated N-donor ligand. The coordination of pyrazine, Bipy, and PySSPy at the antimony atom changes their mechanism of electrooxidation: instead of two successive redox stages Cat/SQ and SQ/Cat, one multielectron stage was observed. The coordination of the DABCO ligand is accompanied by a significant shift in the oxidation potentials of the catecholate ligand to the cathodic region (by 0.4 V), compared to the initial complex.

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“…[ 20 , 21 , 22 , 23 , 24 , 25 ]. Catechol-thioethers are prospective objects from the viewpoint of studying the antioxidant properties of polyfunctional compounds, and are new objects in coordination chemistry [ 26 , 27 , 28 , 29 , 30 , 31 , 32 ]. For example, complexes of 4,6-di-tert-butylcatechol derivatives containing cystamine or cysteine residues at position 3 of such ligands are actively studied [ 26 , 27 ].…”

Section: Introductionmentioning

confidence: 99%

Triphenylantimony(V) Catecholates of the Type (3-RS-4,6-DBCat)SbPh3-Catechol Thioether Derivatives: Structure, Electrochemical Properties, and Antiradical Activity

et al. 2021

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A new series of triphenylantimony(V) 3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh3, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7), and naphthyl-2 (8), were synthesized from the corresponding catechol thioethers and Ph3SbBr2 in the presence of a base. The crystal structures of 1, 2, 3, and 5 were determined by single-crystal X-ray analysis. The coordination polyhedron of 1–3 is better described as a tetragonal pyramid with a different degree of distortion, while that for 5- was a distorted trigonal bipyramid (τ = 0.014, 0.177, 0.26, 0.56, respectively). Complexes demonstrated different crystal packing of molecules. The electrochemical oxidation of the complexes involved the catecholate group as well as the thioether linker. The introduction of a thioether fragment into the aromatic ring of catechol ligand led to a shift in the potential of the “catechol/o-semiquinone” redox transition to the anodic region, which indicated the electron-withdrawing nature of the RS group. The radical scavenging activity of the complexes was determined in the reaction with DPPH radical.

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Polyfunctional Sterically Hindered Catechols with Additional Phenolic Group and Their Triphenylantimony(V) Catecholates: Synthesis, Structure, and Redox Properties

Cited by 13 publications

References 92 publications

Synthesis and Antioxidant Activity of New Catechol Thioethers with the Methylene Linker

Synthesis and Antioxidant Activity of New Catechol Thioethers with the Methylene Linker

Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties

Triphenylantimony(V) Catecholates of the Type (3-RS-4,6-DBCat)SbPh3-Catechol Thioether Derivatives: Structure, Electrochemical Properties, and Antiradical Activity

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