2026-04-28T19:32:10Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/93232024-07-02T00:05:28Zcom_10259_4363com_10259_5086com_10259_2604com_10259_3596col_10259_4364col_10259_3597

Gil García, Rubén 232 600 Madariaga, Gotzon 0f2d197b-c4d0-47fd-9235-e4db4aaa9651 600 Jiménez Pérez, Alondra 789 600 0000-0001-7157-0674 Herrán Torres, Ignacio 66d8c86c-b774-4995-8152-ef877094dc15 600 Gago González, Adrián 9e116628-5749-4cbf-a8a3-b4fbc368c87b 600 Ugalde, María 559 600 Januskaitis, Vaidas 9be2511c-ee11-4084-a41e-ccd72be4ca29 600 Barrera García, Joaquín 3382b6b7-74cd-41e1-91cc-b8cf085622e4 600 Insausti, Maite 76f80144-958c-4b7f-b6e3-e88cf5e2a404 600 Galletero, María S. dc3376b6-9c58-4914-98ba-7ded89492e2d 600 Borrás, Joaquín e76bcd74-c3d7-4997-82a7-59f3c9a26017 600 Cuevas Vicario, José Vicente 137 600 0000-0002-2421-1529 Pedrido Castiñeiras, Rosa 1e897c0c-b8bf-4c88-8068-bfaeb93a928b 600 Gómez Sáiz, Patricia fa27a251-bdb7-4b69-8b73-098ce9aefbca 600 Lezama, Luis 9b1ac1a2-e0b6-4d1f-afe9-c7c94f068da9 600 García Tojal, Javier 221 600 0000-0003-3816-0483 2024-07-01T06:55:06Z 2024-07-01T06:55:06Z 2023-03-06 http://hdl.handle.net/10259/9323 10.1039/D3CE00119A 1466-8033 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. 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. application/pdf eng Royal Society of Chemistry CrystEngComm. 2023, V. 25, n. 15, p. 2213-2226 https://doi.org/10.1039/D3CE00119A Atribución 4.0 Internacional http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess Química inorgánica Chemistry, Inorganic Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion CrystEngComm 25 15 2213 2226 THUMBNAIL Gil-cec_2023.pdf.jpg Gil-cec_2023.pdf.jpg IM Thumbnail image/jpeg 3983 https://riubu.ubu.es/bitstream/10259/9323/4/Gil-cec_2023.pdf.jpg b6e54f815cb84b2e245ee09546f8f00a MD5 4 LICENSE license.txt license.txt text/plain; charset=utf-8 1362 https://riubu.ubu.es/bitstream/10259/9323/3/license.txt 5d013bfa6e473ff0db22cd82a4d71a70 MD5 3 CC-LICENSE license_rdf license_rdf application/rdf+xml; charset=utf-8 908 https://riubu.ubu.es/bitstream/10259/9323/2/license_rdf 0175ea4a2d4caec4bbcc37e300941108 MD5 2 ORIGINAL Gil-cec_2023.pdf Gil-cec_2023.pdf application/pdf 1368239 https://riubu.ubu.es/bitstream/10259/9323/1/Gil-cec_2023.pdf 09fd9e943b85fa062ff4d9dd4f13c54f MD5 1 10259/9323 oai:riubu.ubu.es:10259/9323 2024-07-02 02:05:28.65 Repositorio Institucional de la Universidad de Burgos bubrep@ubu.es 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