Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media

The use of perchlorate ancillary ligands with relatively low coordination ability nicely illustrates a rich structural diversity in thiosemicarbazone copper(II) (TSC-Cu(II)) systems. Five compounds with the formulae {[CuL(OH2)][CuL(OClO3)]}n·nClO4·2nH2O (1), [{CuL(OClO3)}2] (2), [Cu(HL)(OClO3)2(OH2)...

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Autores: Gil García, Rubén, Madariaga, Gotzon, Jiménez Pérez, Alondra, Herrán Torres, Ignacio, Gago González, Adrián, Ugalde, María, Januskaitis, Vaidas, Barrera García, Joaquín, Insausti, Maite, Galletero, María S., Borrás, Joaquín, Cuevas Vicario, José Vicente, Pedrido Castiñeiras, Rosa, Gómez Sáiz, Patricia, Lezama, Luis, García Tojal, Javier
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Universidad de Burgos (UBU)
Repositorio:Repositorio Institucional de la Universidad de Burgos (RIUBU)
OAI Identifier:oai:riubu.ubu.es:10259/9323
Acceso en línea:http://hdl.handle.net/10259/9323
Access Level:acceso abierto
Palabra clave:Química inorgánica
Chemistry, Inorganic
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spelling Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic mediaGil García, RubénMadariaga, GotzonJiménez Pérez, AlondraHerrán Torres, IgnacioGago González, AdriánUgalde, MaríaJanuskaitis, VaidasBarrera García, JoaquínInsausti, MaiteGalletero, María S.Borrás, JoaquínCuevas Vicario, José VicentePedrido Castiñeiras, RosaGómez Sáiz, PatriciaLezama, LuisGarcía Tojal, JavierQuímica inorgánicaChemistry, InorganicThe use of perchlorate ancillary ligands with relatively low coordination ability nicely illustrates a rich structural diversity in thiosemicarbazone copper(II) (TSC-Cu(II)) systems. Five compounds with the formulae {[CuL(OH2)][CuL(OClO3)]}n·nClO4·2nH2O (1), [{CuL(OClO3)}2] (2), [Cu(HL)(OClO3)2(OH2)] H2O (3), [Cu2L3](ClO4)·2H2O (4) and [Cu(HL)(NCS)](ClO4) (5) are studied, where HL = pyridine-2-carbaldehyde thiosemicarbazone. The crystal structures show the presence of polynuclear species in the compounds containing an anionic L− thiosemicarbazone ligand: 1D chains (1) and dinuclear (2 and 4) arrangements. Meanwhile, complexes with a neutral HL ligand give rise to mononuclear entities (3 and 5). The chemical and structural parallelism of these complexes with the analogous TSC–Cu(II)–nitrate system is discussed. The thiocyanate ligand in compound 5 comes from partial desulfurization of the thiosemicarbazone in acid medium and results in an incommensurate modulated structure. On the other hand, it is proposed that [Cu2L3]+ species present in 4 could play a possible role in desulfurization reactions. Experimental evidence and theoretical calculations support a proposed mechanism for the partial desulfurization of preformed TSC-Cu(II) entities in basic and physiological media to yield the [CuL(LCN)] (HLCN = pyridine-2-ylmethylene(hydrazine carbonitrile)) and [{CuL(SH)}2)] compounds.This work was supported by the European Union H2020-LC-SC3-2020-NZE-RES-CC, NMBP-16- 2020-GA 953152 and DT-NMBP-04-2020 Projects, together with Ministerio de Ciencia, Innovación, for the project PID2021- 127531NB-I00 (AEI/10.13039/501100011033/FEDER, UE), PDC2022-133955-I00 and Ministerio de Ciencia, Innovación y Universidades CTQ(QMC) RED2018-102471-T MultiMetDrugs Network (Spain), Consejería de Educación of Junta de Castilla y León and FEDER BU049P20, Fundacion Bancaria Caixa D. Estalvis i Pensions de Barcelona 001 and Ministerio de Ciencia e Innovación PID2019-106644GB-I00 and Gobierno Vasco IT1458-22. R. G.-G. and A. J.-P. wish to thank the Junta de Castilla y León for their Doctoral Fellowships.Royal Society of Chemistry202420242023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10259/9323reponame:Repositorio Institucional de la Universidad de Burgos (RIUBU)instname:Universidad de Burgos (UBU)InglésCrystEngComm. 2023, V. 25, n. 15, p. 2213-2226https://doi.org/10.1039/D3CE00119AAtribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:riubu.ubu.es:10259/93232026-05-28T07:56:11Z
dc.title.none.fl_str_mv Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
title Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
spellingShingle Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
Gil García, Rubén
Química inorgánica
Chemistry, Inorganic
title_short Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
title_full Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
title_fullStr Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
title_full_unstemmed Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
title_sort Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
dc.creator.none.fl_str_mv Gil García, Rubén
Madariaga, Gotzon
Jiménez Pérez, Alondra
Herrán Torres, Ignacio
Gago González, Adrián
Ugalde, María
Januskaitis, Vaidas
Barrera García, Joaquín
Insausti, Maite
Galletero, María S.
Borrás, Joaquín
Cuevas Vicario, José Vicente
Pedrido Castiñeiras, Rosa
Gómez Sáiz, Patricia
Lezama, Luis
García Tojal, Javier
author Gil García, Rubén
author_facet Gil García, Rubén
Madariaga, Gotzon
Jiménez Pérez, Alondra
Herrán Torres, Ignacio
Gago González, Adrián
Ugalde, María
Januskaitis, Vaidas
Barrera García, Joaquín
Insausti, Maite
Galletero, María S.
Borrás, Joaquín
Cuevas Vicario, José Vicente
Pedrido Castiñeiras, Rosa
Gómez Sáiz, Patricia
Lezama, Luis
García Tojal, Javier
author_role author
author2 Madariaga, Gotzon
Jiménez Pérez, Alondra
Herrán Torres, Ignacio
Gago González, Adrián
Ugalde, María
Januskaitis, Vaidas
Barrera García, Joaquín
Insausti, Maite
Galletero, María S.
Borrás, Joaquín
Cuevas Vicario, José Vicente
Pedrido Castiñeiras, Rosa
Gómez Sáiz, Patricia
Lezama, Luis
García Tojal, Javier
author2_role author
author
author
author
author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Química inorgánica
Chemistry, Inorganic
topic Química inorgánica
Chemistry, Inorganic
description The use of perchlorate ancillary ligands with relatively low coordination ability nicely illustrates a rich structural diversity in thiosemicarbazone copper(II) (TSC-Cu(II)) systems. Five compounds with the formulae {[CuL(OH2)][CuL(OClO3)]}n·nClO4·2nH2O (1), [{CuL(OClO3)}2] (2), [Cu(HL)(OClO3)2(OH2)] H2O (3), [Cu2L3](ClO4)·2H2O (4) and [Cu(HL)(NCS)](ClO4) (5) are studied, where HL = pyridine-2-carbaldehyde thiosemicarbazone. The crystal structures show the presence of polynuclear species in the compounds containing an anionic L− thiosemicarbazone ligand: 1D chains (1) and dinuclear (2 and 4) arrangements. Meanwhile, complexes with a neutral HL ligand give rise to mononuclear entities (3 and 5). The chemical and structural parallelism of these complexes with the analogous TSC–Cu(II)–nitrate system is discussed. The thiocyanate ligand in compound 5 comes from partial desulfurization of the thiosemicarbazone in acid medium and results in an incommensurate modulated structure. On the other hand, it is proposed that [Cu2L3]+ species present in 4 could play a possible role in desulfurization reactions. Experimental evidence and theoretical calculations support a proposed mechanism for the partial desulfurization of preformed TSC-Cu(II) entities in basic and physiological media to yield the [CuL(LCN)] (HLCN = pyridine-2-ylmethylene(hydrazine carbonitrile)) and [{CuL(SH)}2)] compounds.
publishDate 2023
dc.date.none.fl_str_mv 2023
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10259/9323
url http://hdl.handle.net/10259/9323
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv CrystEngComm. 2023, V. 25, n. 15, p. 2213-2226
https://doi.org/10.1039/D3CE00119A
dc.rights.none.fl_str_mv Atribución 4.0 Internacional
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Atribución 4.0 Internacional
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:Repositorio Institucional de la Universidad de Burgos (RIUBU)
instname:Universidad de Burgos (UBU)
instname_str Universidad de Burgos (UBU)
reponame_str Repositorio Institucional de la Universidad de Burgos (RIUBU)
collection Repositorio Institucional de la Universidad de Burgos (RIUBU)
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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