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

A series of binuclear triphenylantimony(V) bis-catecholato complexes 1–11 of the type (Cat)Ph(3)Sb-linker-SbPh(3)(Cat) was prepared by a reaction of the corresponding mononuclear catecholates (Cat)SbPh(3) with a neutral bidentate donor linker ligands pyrazine (Pyr), 4,4′-dipyridyl (Bipy), bis-(pyrid...

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Autores principales: Poddel’sky, Andrey I., Smolyaninov, Ivan V., Shataeva, Aleksandra I., Baranov, Evgenii V., Fukin, Georgy K.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
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Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9573088/
https://www.ncbi.nlm.nih.gov/pubmed/36235022
http://dx.doi.org/10.3390/molecules27196484
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author Poddel’sky, Andrey I.
Smolyaninov, Ivan V.
Shataeva, Aleksandra I.
Baranov, Evgenii V.
Fukin, Georgy K.
author_facet Poddel’sky, Andrey I.
Smolyaninov, Ivan V.
Shataeva, Aleksandra I.
Baranov, Evgenii V.
Fukin, Georgy K.
author_sort Poddel’sky, Andrey I.
collection PubMed
description A series of binuclear triphenylantimony(V) bis-catecholato complexes 1–11 of the type (Cat)Ph(3)Sb-linker-SbPh(3)(Cat) was prepared by a reaction of the corresponding mononuclear catecholates (Cat)SbPh(3) 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-Cl(2)-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-Cl(2)-3,6-DBCat)SbPh(3) with DABCO in an open atmosphere results in a formation of 1D coordination polymer {[(4,5-Cl(2)-3,6-DBCat)SbPh(3)·H(2)O]·DABCO}(n) (12). Bis-catecholate complex Ph(3)Sb(Cat-Spiro-Cat)SbPh(3) reacts with Bipy as 1:1 yielding a rare macrocyclic tetranuclear compound {Ph(3)Sb(Cat-Spiro-Cat)SbPh(3)∙(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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spelling pubmed-95730882022-10-17 Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties Poddel’sky, Andrey I. Smolyaninov, Ivan V. Shataeva, Aleksandra I. Baranov, Evgenii V. Fukin, Georgy K. Molecules Article A series of binuclear triphenylantimony(V) bis-catecholato complexes 1–11 of the type (Cat)Ph(3)Sb-linker-SbPh(3)(Cat) was prepared by a reaction of the corresponding mononuclear catecholates (Cat)SbPh(3) 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-Cl(2)-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-Cl(2)-3,6-DBCat)SbPh(3) with DABCO in an open atmosphere results in a formation of 1D coordination polymer {[(4,5-Cl(2)-3,6-DBCat)SbPh(3)·H(2)O]·DABCO}(n) (12). Bis-catecholate complex Ph(3)Sb(Cat-Spiro-Cat)SbPh(3) reacts with Bipy as 1:1 yielding a rare macrocyclic tetranuclear compound {Ph(3)Sb(Cat-Spiro-Cat)SbPh(3)∙(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. MDPI 2022-10-01 /pmc/articles/PMC9573088/ /pubmed/36235022 http://dx.doi.org/10.3390/molecules27196484 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Poddel’sky, Andrey I.
Smolyaninov, Ivan V.
Shataeva, Aleksandra I.
Baranov, Evgenii V.
Fukin, Georgy K.
Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties
title Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties
title_full Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties
title_fullStr Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties
title_full_unstemmed Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties
title_short Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties
title_sort binuclear triphenylantimony(v) catecholates through n-donor linkers: structural features and redox properties
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9573088/
https://www.ncbi.nlm.nih.gov/pubmed/36235022
http://dx.doi.org/10.3390/molecules27196484
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