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Trends in properties of para-substituted 3-(phenylhydrazo)pentane-2,4-diones

2011-09Journal article Open access
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dc.contributor.authorKopylovich, Maximilian
dc.contributor.authorMahmudov, Kamran
dc.contributor.authorGuedes Da Silva, M. Fátima C.
dc.contributor.authorMartins, Luisa
dc.contributor.authorKuznetsov, Maxim L.
dc.contributor.authorSilva, Telma F. S.
dc.contributor.authorFraústo Da Silva, João
dc.contributor.authorPombeiro, Armando
dc.date.accessioned2013-02-17T13:38:20Z
dc.date.available2013-02-17T13:38:20Z
dc.date.issued2011-09
dc.description.abstractTrends between the Hammett's sigma(p) and related normal sigma(n)(p), inductive sigma(I), resonance sigma(R), negative sigma(-)(p) and positive sigma(+)(p) polar conjugation and Taft's sigma(o)(p) substituent constants and the N-H center dot center dot center dot O distance, delta(N-H) NMR chemical shift, oxidation potential (E-p/2(ox), measured in this study by cyclic voltammetry (CV)) and thermodynamic parameters (pK, Delta G(0), Delta H-0 and Delta S-0) of the dissociation process of unsubstituted 3-(phenylhydrazo)pentane-2,4-dione (HL1) and its para-substituted chloro (HL2), carboxy (HL3), fluoro (HL4) and nitro (HL5) derivatives were recognized. The best fits were found for sigma(p) and/or sigma(-)(p) in the cases of d(N center dot center dot center dot O), delta(N-H) and E-p/2(ox), showing the importance of resonance and conjugation effects in such properties, whereas for the above thermodynamic properties the inductive effects (sigma(I)) are dominant. HL2 exists in the hydrazo form in DMSO solution and in the solid state and contains an intramolecular H-bond with the N center dot center dot center dot O distance of 2.588(3)angstrom. It was also established that the dissociation process of HL1-5 is non-spontaneous, endothermic and entropically unfavourable, and that the increase in the inductive effect (sigma(I)) of para-substitutents (-H < -Cl < -COOH < -F < -NO2) leads to the corresponding growth of the N center dot center dot center dot O distance and decrease of the pK and of the changes of Gibbs free energy, of enthalpy and of entropy for the HL1-5 acid dissociation process. The electrochemical behaviour of HL1-5 was interpreted using theoretical calculations at the DFT/HF hybrid level, namely in terms of HOMO and LUMO compositions, and of reactivities induced by anodic and cathodic electron-transfers. Copyright (C) 2010 John Wiley & Sons, Ltd.por
dc.identifier.citationKOPYLOVICH, Maximilian N.; MAHMUDOV, Kamran T.; GUEDES DA SILVA, M. Fátima C.; MARTINS, Luísa M. D. R. S.; KUZNETSOV, Maxim L.; SILVA, Telma F. S.; FRAÚSTO DA SILVA, João J. R.; POMBEIRO, Armando J. L. - Trends in properties of para-substituted 3-(phenylhydrazo)pentane-2,4-diones. Journal of Physical Organic Chemistry. ISSN 0894-3230. Vol. 24, n.º 9 (2011) p. 764-773.por
dc.identifier.issn0894-3230
dc.identifier.urihttp://hdl.handle.net/10400.21/2256
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherWiley-Blackwellpor
dc.subject3-(4-Substituted Phenylhydrazo)Pentane-2,4-Dionespor
dc.subjectCorrelation Analysispor
dc.subjectDFT Calculationspor
dc.subjectRedox Potentialpor
dc.subjectTautomerspor
dc.subjectThermodynamic Parameterspor
dc.subjectStructure-Reactivity Parameterspor
dc.subjectRuthenium Anticancer Drugspor
dc.subjectSubstituted Benzoic-Acidspor
dc.subjectBeta-Diketonespor
dc.subjectCrystal-Structurepor
dc.subjectRedox Propertiespor
dc.subjectPotential Antineoplasticspor
dc.subjectCoordination-Compoundspor
dc.subjectFerrocene Derivativespor
dc.subjectElectron-Transferpor
dc.titleTrends in properties of para-substituted 3-(phenylhydrazo)pentane-2,4-dionespor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.conferencePlaceMaldenpor
oaire.citation.endPage773por
oaire.citation.issue9por
oaire.citation.startPage764por
oaire.citation.titleJournal of Physical Organic Chemistrypor
oaire.citation.volume24por
person.familyNameKopylovich
person.familyNameMahmudov
person.familyNameGuedes da Silva
person.familyNameMartins
person.familyNameKuznetsov
person.familyNameFraústo da Silva
person.familyNamePombeiro
person.givenNameMaximilian
person.givenNameKamran
person.givenNameM. Fátima C.
person.givenNameLuisa
person.givenNameMaxim L.
person.givenNameJoão
person.givenNameArmando
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rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
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