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

ABSTRACT: New polyfunctional sterically hindered 3,5-di-tert-butylcatechols with an additional phenolic group in the sixth position connected by a bridging sulfur atom-(6-(CH₂-S-tBu₂Phenol)-3,5-DBCat)H₂ (L₁), (6-(S-tBu₂Phenol)-3,5-DBCat)H₂ (L₂), and (6-(S-Phenol)-3,5-DBCat)H₂ (L₃) (3,5-DBCat is dianion 3,5-di-tert-butylcatecolate)-were synthesized and characterized in detail. The exchange reaction between catechols L₁ and L₃ with triphenylantimony(V) dibromide in the presence of triethylamine leads to the corresponding triphenylantimony(V) catecholates (6-(CH₂-S-tBu₂Phenol)-3,5-DBCat)SbPh₃ (1) and (6-(S-Phenol)-3,5-DBCat)SbPh₃ (2). The electrochemical properties of catechols L₁-L₃ and catecholates 1 and 2 were investigated using cyclic voltammetry. The electrochemical oxidation of L₁-L₃ at the first stage proceeds with the formation of the corresponding o-benzoquinones. The second process is the oxidation of the phenolic moiety. Complexes 1 and 2 significantly expand their redox capabilities, owing to the fact that they can act as the electron donors due to the catecholate metallocycle capable of sequential oxidations, and as donors of the hydrogen atoms, thus forming a stable phenoxyl radical. The molecular structures of the free ligand L₁ and complex 1 in the crystal state were determined by single-crystal X-ray analysis.

SUBMITTER: Smolyaninov IV

PROVIDER: S-EPMC7221534 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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

Smolyaninov Ivan V IV Poddel'sky Andrey I AI Smolyaninova Susanna A SA Arsenyev Maxim V MV Fukin Georgy K GK Berberova Nadezhda T NT

Molecules (Basel, Switzerland) 20200412 8

New polyfunctional sterically hindered 3,5-di-tert-butylcatechols with an additional phenolic group in the sixth position connected by a bridging sulfur atom-(6-(CH2-S-tBu2Phenol)-3,5-DBCat)H2 (L1), (6-(S-tBu2Phenol)-3,5-DBCat)H2 (L2), and (6-(S-Phenol)-3,5-DBCat)H2 (L3) (3,5-DBCat is dianion 3,5-di-tert-butylcatecolate)-were synthesized and characterized in detai ...[more]

PMID: 32290617

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Project description: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.

Dataset Information

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

Publications

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

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