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A bis(mu-chlorido)-bridged cobalt(II) complex with silyl-containing schiff base as a catalyst precursor in the solvent-free oxidation of cyclohexane

2017-10Journal article Restricted access
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dc.contributor.authorZaltariov, Mirela-Fernanda
dc.contributor.authorVieru, Veacheslav
dc.contributor.authorZalibera, Michal
dc.contributor.authorCazacu, Maria
dc.contributor.authorMartins, Nuno M. R.
dc.contributor.authorMartins, Luisa
dc.contributor.authorRapta, Peter
dc.contributor.authorNOVITCHI, Ghenadie
dc.contributor.authorShova, Sergiu
dc.contributor.authorPombeiro, Armando
dc.contributor.authorArion, Vladimir B.
dc.date.accessioned2017-11-10T14:24:32Z
dc.date.available2017-11-10T14:24:32Z
dc.date.issued2017-10
dc.description.abstractA new bis(µ-chlorido)-bridged cobalt(II) complex [Co2(µ-Cl)2(HL2)4][CoCl4] (1), where HL2 is a silyl-containing Schiff base, was synthesised. The structure of this compound was established by X-ray crystallography revealing a zwitterionic form adopted by the organic ligand. The temperature dependence of the magnetic susceptibility and the field dependence of the magnetisation indicate the presence of ferromagnetic interactions between paramagnetic d7 cobalt(II) centres (SCo = 3/2). The exchange coupling parameter J(Co1–Co2) = +7.0 cm–1 extracted from broken-symmetry (BS) DFT calculations agrees well with the value of +8.8 cm–1 determined from the experimental data by fitting them with the Hamiltonian math formula. Electrochemical studies indicate that complex 1 is inefficient as a catalyst in electrochemical reduction of protons. One of the reasons is the low stability of the complex in solution. In contrast, 1 acts as an effective homogeneous (pre)catalyst in the microwave-assisted neat oxidation of cyclohexane with aqueous tBuOOH (TBHP). The possible mechanism of catalytic oxidation and other advantages of using 1 in the oxidation of cycloalkanes are discussed.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationZALTARIOV, Mirela-Fernanda [et al] - A Bis(mu-chlorido)-Bridged Cobalt(II) Complex with Silyl-Containing Schiff Base as a Catalyst Precursor in the Solvent-Free Oxidation of Cyclohexane. European Journal Of Inorganic Chemistry. ISSN 1434-1948. Vol. 37 (2017), pp. 4324-4332pt_PT
dc.identifier.doi10.1002/ejic.201700875pt_PT
dc.identifier.issn1434-1948
dc.identifier.issn1099-0682
dc.identifier.urihttp://hdl.handle.net/10400.21/7482
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherWILEY-V C H VERLAG GMBHpt_PT
dc.relationSFRH/BD/52371/2013pt_PT
dc.relation.publisherversionhttp://onlinelibrary.wiley.com/doi/10.1002/ejic.201700875/epdfpt_PT
dc.subjectCobaltpt_PT
dc.subjectSiliconpt_PT
dc.subjectSchiff basespt_PT
dc.subjectCatalyst precursorspt_PT
dc.subjectOxidationpt_PT
dc.subjectCyclohexanept_PT
dc.titleA bis(mu-chlorido)-bridged cobalt(II) complex with silyl-containing schiff base as a catalyst precursor in the solvent-free oxidation of cyclohexanept_PT
dc.typejournal article
dspace.entity.typePublication
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/3599-PPCDT/PTDC%2FQEQ-ERQ%2F1648%2F2014/PT
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/3599-PPCDT/PTDC%2FQEQ-QIN%2F3967%2F2014/PT
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/5876/UID%2FQUI%2F00100%2F2013/PT
oaire.citation.endPage4332pt_PT
oaire.citation.startPage4324pt_PT
oaire.citation.titleEuropean Journal of Inorganic Chemistrypt_PT
oaire.citation.volume37pt_PT
oaire.fundingStream3599-PPCDT
oaire.fundingStream3599-PPCDT
oaire.fundingStream5876
person.familyNameVieru
person.familyNameZalibera
person.familyNameCazacu
person.familyNameMartins
person.familyNameRapta
person.familyNameNOVITCHI
person.familyNamePombeiro
person.givenNameVeacheslav
person.givenNameMichal
person.givenNameMaria
person.givenNameLuisa
person.givenNamePeter
person.givenNameGhenadie
person.givenNameArmando
person.identifier637885
person.identifier.ciencia-idE218-E297-A4EA
person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0001-6375-4537
person.identifier.orcid0000-0002-6527-1982
person.identifier.orcid0000-0003-4952-5548
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0001-6071-3932
person.identifier.orcid0000-0002-6109-6937
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridA-1591-2017
person.identifier.ridG-6210-2011
person.identifier.ridH-3606-2013
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id8621556700
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id7006067269
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
project.funder.nameFundação para a Ciência e a Tecnologia
project.funder.nameFundação para a Ciência e a Tecnologia
rcaap.rightsclosedAccesspt_PT
rcaap.typearticlept_PT
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