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Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

2011Journal article Open access
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dc.contributor.authorKopylovich, Maximilian N.
dc.contributor.authorNunes, Andreia C. C.
dc.contributor.authorMahmudov, Kamran
dc.contributor.authorHaukka, Matti
dc.contributor.authorMac Leod, Tatiana C. O.
dc.contributor.authorMartins, Luisa
dc.contributor.authorKuznetsov, Maxim L.
dc.contributor.authorPombeiro, Armando
dc.date.accessioned2013-01-31T12:46:44Z
dc.date.available2013-01-31T12:46:44Z
dc.date.issued2011
dc.description.abstractReactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.por
dc.identifier.citationKOPYLOVICH, Maximilian N.; NUNES, Andreia C. C.; MAHMUDOV, Kamran T.; HAUKKA, Matti; MAC LEOD, Tatiana C. O.; MARTINS, Luisa M. D. R. S.; KUZNETSOV, Maxim L.; POMBEIRO, Armando J. L. - Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation. Dalton Transactions. Vol. 40, n.º 12 (2011) p. 2822-2836.por
dc.identifier.issn1477-9226
dc.identifier.urihttp://hdl.handle.net/10400.21/2122
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherRoyal Soc Chemistrypor
dc.subjectMild Peroxidative Oxidationpor
dc.subjectO-2-H2O2-Vanadium Derivative-Pyrazine-2-Carboxylic Acidpor
dc.subjectHydrogen-Peroxidepor
dc.subjectCrystal-Structurespor
dc.subjectBeta-Diketonespor
dc.subjectTriethanolamine Complexespor
dc.subjectPotential Antineoplasticspor
dc.subjectHydrocarbon Oxygenationspor
dc.subjectAzo Derivativespor
dc.subjectAlkanespor
dc.titleComplexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidationpor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.conferencePlaceCambridgepor
oaire.citation.endPage2836por
oaire.citation.issue12por
oaire.citation.startPage2822por
oaire.citation.titleDalton Transactionspor
oaire.citation.volume40por
person.familyNameKopylovich
person.familyNameMahmudov
person.familyNameHaukka
person.familyNameMartins
person.familyNameKuznetsov
person.familyNamePombeiro
person.givenNameMaximilian
person.givenNameKamran
person.givenNameMatti
person.givenNameLuisa
person.givenNameMaxim L.
person.givenNameArmando
person.identifier637885
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person.identifier.ciencia-idCD1F-CB64-9EA5
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person.identifier.orcid0000-0002-6744-7208
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0001-5729-6189
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridH-8625-2012
person.identifier.ridI-1409-2013
person.identifier.ridG-6210-2011
person.identifier.ridH-7934-2012
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person.identifier.scopus-author-id7003887561
person.identifier.scopus-author-id24468352000
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id7102379353
person.identifier.scopus-author-id7006067269
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
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