Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.21/7366
Registo completo
Campo DCValorIdioma
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 M. D. R. S.-
dc.contributor.authorPombeiro, Armando J. L.-
dc.contributor.authorArion, Vladimir B.-
dc.date.accessioned2017-09-05T14:08:37Z-
dc.date.available2017-09-05T14:08:37Z-
dc.date.issued2016-09-
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, Nº.18, (2016), pp 9187-9203.pt_PT
dc.identifier.issn0020-1669-
dc.identifier.issn1520-510X-
dc.identifier.urihttp://hdl.handle.net/10400.21/7366-
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.language.isoengpt_PT
dc.publisherAmerican Chemical Societypt_PT
dc.rightsclosedAccesspt_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.typearticlept_PT
dc.peerreviewedyespt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
degois.publication.firstPage9187pt_PT
degois.publication.lastPage9203pt_PT
degois.publication.issue18pt_PT
degois.publication.titleInorganic Chemistrypt_PT
degois.publication.volume55pt_PT
dc.identifier.doi10.1021/acs.inorgchem.6b01011pt_PT
Aparece nas colecções:ISEL - Eng. Quim. Biol. - Artigos

Ficheiros deste registo:
Ficheiro Descrição TamanhoFormato 
VanadiumV_LMDRSMartins_ADEQ.pdf5,35 MBAdobe PDFVer/Abrir    Acesso Restrito. Solicitar cópia ao autor!


FacebookTwitterDeliciousLinkedInDiggGoogle BookmarksMySpace
Formato BibTex MendeleyEndnote Degois 

Todos os registos no repositório estão protegidos por leis de copyright, com todos os direitos reservados.