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Vanadium(V) complexes with substituted 1,5-bis(2- hydroxybenzaldehyde)carbohydrazones and their use as catalyst precursors in oxidation of cyclohexane

2016-09Journal article Restricted access
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dc.contributor.authorDragancea, Diana
dc.contributor.authorTalmaci, Natalia
dc.contributor.authorShova, Sergiu
dc.contributor.authorNOVITCHI, Ghenadie
dc.contributor.authorDarvasiova, Denisa
dc.contributor.authorRapta, Peter
dc.contributor.authorBreza, Martin
dc.contributor.authorGalanski, Markus
dc.contributor.authorKozisek, Jozef
dc.contributor.authorMartins, Nuno M. R.
dc.contributor.authorMartins, Luisa
dc.contributor.authorPombeiro, Armando
dc.contributor.authorArion, Vladimir B.
dc.date.accessioned2017-09-05T14:08:37Z
dc.date.available2017-09-05T14:08:37Z
dc.date.issued2016-09
dc.description.abstractSix dinuclear vanadium(V) complexes have been synthesized: NH4[(VO2)(2)((LH)-L-H)] (NH4[1]), NH4[(VO2)(2)((LH)-L-tBu)] (NH4[2]), NH4[(VO2)(2)((LH)-L-Cl)] (NH4[3]), [(VO2)(2)(VO) ((LH)-L-H) (CH3O)] (4), [(VO2) (VO) (t-BuLH) (C2H5O)] (5), and [ (VO2) (VO) (Cl-LH) (CH3O)(CH3OH/H2O)] (6) (where (LH4)-L-H = 1,5-bis(2-hydroxybenzaldehyde)carb ohydrazon e, t-BuLH4 = 1,5-bis(3,5-di-tert-butyl-2-hydroxybenzaldehyde) carbohydrazone, and (LH4)-L-cl = 1,5-bis(3,5-dichloro-2-hydroxybenzaldehyde)carbohydrazone). The structures of NH4[1] and 4-6 have been determined by X-ray diffraction (XRD) analysis. In all complexes, the triply deprotonated ligand accommodates two V ions, using two different binding sites ONN and ONO separated by a diazine unit -N-N-. In two pockets of NH4[1], two identical VO2+ entities are present, whereas, in those of 4-6, two different VO2+ and VO3+ are bound. The highest oxidation state of V ions was corroborated by X-ray data, indicating the presence of alkoxido ligand bound to VO3+ in 4-6, charge density measurements on 4, magnetic susceptibility, NMR spectroscopy, spectroelectrochemistry, and density functional theory (DFT) calculations. All four complexes characterized by XRD form dimeric associates in the solid state, which, however, do not remain intact in solution. Compounds NH4[1], NH4[2], and 4-6 were applied as alternative selective homogeneous catalysts for the industrially significant oxidation of cyclohexane to cyclohexanol and cyclohexanone. The peroxidative (with tert-butyl hydroperoxide, TBHP) oxidation of cyclohexane was performed under solvent -free and additive -free conditions and under low-power microwave (MW) irradiation. Cyclohexanol and cyclohexanone were the only products obtained (high selectivity), after 1.5 h of MW irradiation. Theoretical calculations suggest a key mechanistic role played by the carbohydrazone ligand, which can undergo reduction, instead of the metal itself, to form an active reduced form of the catalyst.pt_PT
dc.description.sponsorshipPTDC/QEQERQ/1648/2014
dc.description.sponsorshipPTDC/QEQ-QIN/3967/2014
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationDRAGANCEA, D. [et all] - Vanadium(V) complexes with substituted 1,5-bis(2- hydroxybenzaldehyde)carbohydrazones and their use as catalyst precursors in oxidation of cyclohexane. inorganic chemistry. ISSN 0020-1669. Vol. 55, N. º18 (2016), pp. 9187-9203pt_PT
dc.identifier.doi10.1021/acs.inorgchem.6b01011pt_PT
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttp://hdl.handle.net/10400.21/7366
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherAmerican Chemical Societypt_PT
dc.titleVanadium(V) complexes with substituted 1,5-bis(2- hydroxybenzaldehyde)carbohydrazones and their use as catalyst precursors in oxidation of cyclohexanept_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage9203pt_PT
oaire.citation.issue18pt_PT
oaire.citation.startPage9187pt_PT
oaire.citation.titleInorganic Chemistrypt_PT
oaire.citation.volume55pt_PT
person.familyNameShova
person.familyNameNOVITCHI
person.familyNameDarvasiova
person.familyNameRapta
person.familyNameBreza
person.familyNameGalanski
person.familyNameKozisek
person.familyNameMartins
person.familyNamePombeiro
person.givenNameSergiu
person.givenNameGhenadie
person.givenNameDenisa
person.givenNamePeter
person.givenNameMartin
person.givenNameMarkus
person.givenNameJozef
person.givenNameLuisa
person.givenNameArmando
person.identifier637885
person.identifier.ciencia-idE218-E297-A4EA
person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0002-1222-4373
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person.identifier.orcid0000-0001-6071-3932
person.identifier.orcid0000-0001-5995-0279
person.identifier.orcid0000-0001-7965-7379
person.identifier.orcid0000-0003-4834-6636
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridH-3606-2013
person.identifier.ridG-6210-2011
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id6701404110
person.identifier.scopus-author-id56695229000
person.identifier.scopus-author-id7005571615
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id7006067269
rcaap.rightsclosedAccesspt_PT
rcaap.typearticlept_PT
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