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Cobalt complexes with pyrazole ligands as catalyst precursors for the peroxidative oxidation of cyclohexane: Z-ray absorption spectroscopy studies and biological applications

2014-04Journal article Restricted access
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dc.contributor.authorSilva, Telma F. S.
dc.contributor.authorMartins, Luisa
dc.contributor.authorGuedes Da Silva, M. Fátima C.
dc.contributor.authorKuznetsov, Maxim L.
dc.contributor.authorFernandes, Alexandra R.
dc.contributor.authorSilva, Ana
dc.contributor.authorPan, Chun-Jern
dc.contributor.authorLee, Jyh-Fu
dc.contributor.authorHwang, Bing Joe
dc.contributor.authorPombeiro, Armando
dc.date.accessioned2015-08-24T10:28:47Z
dc.date.available2015-08-24T10:28:47Z
dc.date.issued2014-04
dc.description.abstract[CoCl(-Cl)(Hpz(Ph))(3)](2) (1) and [CoCl2(Hpz(Ph))(4)] (2) were obtained by reaction of CoCl2 with HC(pz(Ph))(3) and Hpz(Ph), respectively (Hpz(Ph)=3-phenylpyrazole). The compounds were isolated as air-stable solids and fully characterized by IR and far-IR spectroscopy, MS(ESI+/-), elemental analysis, cyclic voltammetry (CV), controlled potential electrolysis, and single-crystal X-ray diffraction. Electrochemical studies showed that 1 and 2 undergo single-electron irreversible (CoCoIII)-Co-II oxidations and (CoCoI)-Co-II reductions at potentials measured by CV, which also allowed, in the case of dinuclear complex 1, the detection of electronic communication between the Co centers through the chloride bridging ligands. The electrochemical behavior of models of 1 and 2 were also investigated by density functional theory (DFT) methods, which indicated that the vertical oxidation of 1 and 2 (that before structural relaxation) affects mostly the chloride and pyrazolyl ligands, whereas adiabatic oxidation (that after the geometry relaxation) and reduction are mostly metal centered. Compounds 1 and 2 and, for comparative purposes, other related scorpionate and pyrazole cobalt complexes, exhibit catalytic activity for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone under mild conditions (room temperature, aqueous H2O2). Insitu X-ray absorption spectroscopy studies indicated that the species derived from complexes 1 and 2 during the oxidation of cyclohexane (i.e., Ox-1 and Ox-2, respectively) are analogous and contain a Co-III site. Complex 2 showed low invitro cytotoxicity toward the HCT116 colorectal carcinoma and MCF7 breast adenocarcinoma cell lines.por
dc.identifier.citationSILVA, Telma F. S.; [et al] – Cobalt complexes with pyrazole ligands as catalyst precursors for the peroxidative oxidation of Cyclohexane: Z-Ray absorption spectroscopy studies and biological applications. Chemistry – An Asian Journal. ISSN: 1861-4728. Vol. 9, nr. 4 (2014), pp. 1132-1143por
dc.identifier.doi10.1002/asia.201301331
dc.identifier.issn1861-4728
dc.identifier.issn1861-471X
dc.identifier.urihttp://hdl.handle.net/10400.21/4927
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherWiley-V C H Verlag GMBHpor
dc.subjectCobaltpor
dc.subjectCyclic voltammetrypor
dc.subjectCyclohexane oxidationpor
dc.subjectInvitro cytotoxicitypor
dc.subjectPyrazole based ligandspor
dc.subjectX-ray absorption spectroscopypor
dc.titleCobalt complexes with pyrazole ligands as catalyst precursors for the peroxidative oxidation of cyclohexane: Z-ray absorption spectroscopy studies and biological applicationspor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.conferencePlaceWeinheimpor
oaire.citation.endPage1143por
oaire.citation.issue4por
oaire.citation.startPage1132por
oaire.citation.titleChemistry – An Asian Journalpor
oaire.citation.volume9por
person.familyNameMartins
person.familyNameGuedes da Silva
person.familyNameLee
person.familyNameHwang
person.familyNamePombeiro
person.givenNameLuisa
person.givenNameM. Fátima C.
person.givenNameJyh-Fu
person.givenNameBing Joe
person.givenNameArmando
person.identifier637885
person.identifier789079
person.identifier.ciencia-idE218-E297-A4EA
person.identifier.ciencia-id7619-8E8E-979A
person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0003-4836-2409
person.identifier.orcid0000-0002-3590-7142
person.identifier.orcid0000-0002-3873-2149
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridG-6210-2011
person.identifier.ridH-8274-2012
person.identifier.ridA-4553-2010
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id6701761571
person.identifier.scopus-author-id7006067269
rcaap.rightsclosedAccesspor
rcaap.typearticlepor
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