2026-06-20T06:49:58Zhttps://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

00925njm 22002777a 4500 dc Gil García, Rubén author Madariaga, Gotzon author Jiménez Pérez, Alondra author Herrán Torres, Ignacio author Gago González, Adrián author Ugalde, María author Januskaitis, Vaidas author Barrera García, Joaquín author Insausti, Maite author Galletero, María S. author Borrás, Joaquín author Cuevas Vicario, José Vicente author Pedrido Castiñeiras, Rosa author Gómez Sáiz, Patricia author Lezama, Luis author García Tojal, Javier author 2023-03-06 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. http://hdl.handle.net/10259/9323 10.1039/D3CE00119A 1466-8033 Perchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic media