RT info:eu-repo/semantics/article
T1 Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media
A1 Gil García, Rubén
A1 Madariaga, Gotzon
A1 Jiménez Pérez, Alondra
A1 Herrán Torres, Ignacio
A1 Gago González, Adrián
A1 Ugalde, María
A1 Januskaitis, Vaidas
A1 Barrera García, Joaquín
A1 Insausti, Maite
A1 Galletero, María S.
A1 Borrás, Joaquín
A1 Cuevas Vicario, José Vicente
A1 Pedrido Castiñeiras, Rosa
A1 Gómez Sáiz, Patricia
A1 Lezama, Luis
A1 García Tojal, Javier
K1 Química inorgánica
K1 Chemistry, Inorganic
AB 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.
PB Royal Society of Chemistry
YR 2023
FD 2023-03-06
LK http://hdl.handle.net/10259/9323
UL http://hdl.handle.net/10259/9323
LA eng
NO 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.
DS Repositorio Institucional de la Universidad de Burgos
RD 22-dic-2024