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dc.contributor.author Maiti, Biplab K.
dc.contributor.author Maia, Luisa B.
dc.contributor.author Pal, Kuntal
dc.contributor.author Pakhira, Bholanath
dc.contributor.author Avilés,Teresa
dc.contributor.author Moura, Isabel
dc.contributor.author Pauleta, Sofia R.
dc.contributor.author Nuñez, José L.
dc.contributor.author Rizzi, Alberto Claudio
dc.contributor.author Brondino, Carlos Dante
dc.contributor.author Sarkar, Sabyasachi
dc.contributor.author Moura, José J. G.
dc.date.available 2017-12-26T18:32:33Z
dc.date.issued 2014-12
dc.identifier.citation Maia, Luisa B.; Moura, José J. G.; Sarkar, Sabyasachi; Brondino, Carlos Dante; Nuñez, José L.; Pauleta, Sofia R.; et al.; One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−; American Chemical Society; Inorganic Chemistry; 53; 24; 12-2014; 12799-12808
dc.identifier.issn 0020-1669
dc.identifier.uri http://hdl.handle.net/11336/31553
dc.description.abstract The complex [Ph4P]2[Cu(bdt)2] (1red) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1red is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1ox). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV–visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1red during its synthesis, since in its absence, 1ox is isolated. Both 1red and 1ox were structurally characterized by X-ray crystallography. EPR experiments showed that 1red is a Cu(II)–sulfur complex and revealed strong covalency on the copper–sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1red has a “thiyl radical character”. Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1red is better described by the two isoelectronic structures [CuI(bdt2, 4S3–,*)]2– ↔ [CuII(bdt2, 4S4–)]2–. On thermodynamic grounds, oxidation of 1red (doublet state) leads to 1ox singlet state, [CuIII(bdt2, 4S4–)]1–.
dc.format application/pdf
dc.language.iso eng
dc.publisher American Chemical Society
dc.rights info:eu-repo/semantics/restrictedAccess
dc.rights.uri https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject Copper
dc.subject EPR
dc.subject.classification Otras Ciencias Químicas
dc.subject.classification Ciencias Químicas
dc.subject.classification CIENCIAS NATURALES Y EXACTAS
dc.title One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
dc.type info:eu-repo/semantics/article
dc.type info:ar-repo/semantics/artículo
dc.type info:eu-repo/semantics/publishedVersion
dc.date.updated 2017-12-21T14:09:14Z
dc.journal.volume 53
dc.journal.number 24
dc.journal.pagination 12799-12808
dc.journal.pais Estados Unidos
dc.journal.ciudad Washington, DC
dc.description.fil Fil: Maiti, Biplab K.. Universidade Nova de Lisboa; Portugal
dc.description.fil Fil: Maia, Luisa B.. Universidade Nova de Lisboa; Portugal
dc.description.fil Fil: Pal, Kuntal. University of Manchester; Reino Unido
dc.description.fil Fil: Pakhira, Bholanath. Indian Institute of Engineering Science and Technology; India
dc.description.fil Fil: Avilés,Teresa. Universidade Nova de Lisboa; Portugal
dc.description.fil Fil: Moura, Isabel. Universidade Nova de Lisboa; Portugal
dc.description.fil Fil: Pauleta, Sofia R.. Universidade Nova de Lisboa; Portugal
dc.description.fil Fil: Nuñez, José L.. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
dc.description.fil Fil: Rizzi, Alberto Claudio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
dc.description.fil Fil: Brondino, Carlos Dante. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
dc.description.fil Fil: Sarkar, Sabyasachi. Indian Institute of Engineering Science and Technology; India
dc.description.fil Fil: Moura, José J. G.. Universidade Nova de Lisboa; Portugal
dc.journal.title Inorganic Chemistry
dc.relation.alternativeid info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ic501742j
dc.relation.alternativeid info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/ic501742
dc.conicet.fuente unificacion


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info:eu-repo/semantics/restrictedAccess Excepto donde se diga explícitamente, este item se publica bajo la siguiente descripción: Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Unported (CC BY-NC-SA 2.5)