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η6-(2-phenoxyethanol) ruthenium(II)-complexes of 2,2′-bipyridine and its derivatives: Solution speciation and kinetic behaviour

2016-10-01Journal article Restricted access
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dc.contributor.authorNogueira, Guilherme
dc.contributor.authorDomotor, Orsolya
dc.contributor.authorPilon, Adhan
dc.contributor.authorRobalo, Maria Paula
dc.contributor.authorAvecilla, Fernando
dc.contributor.authorGarcia, M. Helena
dc.contributor.authorEnyedy, Eva Anna
dc.contributor.authorValente, Andreia
dc.date.accessioned2019-02-21T12:45:52Z
dc.date.available2019-02-21T12:45:52Z
dc.date.issued2016-10-01
dc.description.abstractA novel family of Ru-II-arene compounds with the general formula of [Ru-II(eta(6)-(2-phenoxyethanol))(L) Cl](+) (L: 2,2'-bipyridine (bpy) (3), 4,4'-dimethyl-2,2'-bipyridine (4) and 4,4'-diyldimethanol-2,2'-bipyridine (5)) was synthesized and characterized by standard spectroscopic and analytical methods. Complex 3 was further studied by single-crystal X-ray diffraction analysis, showing a pseudo octahedral geometry and strong pi-pi lateral stacking interactions in the crystal packing. Effect of the substituents on the electrochemical properties and on the aqueous solution stability was monitored by cyclic voltammetry, UV-Vis and H-1 NMR spectroscopy. Complexes 3-5 presented multiple irreversible redox processes according to their cyclic voltammograms recorded in acetonitrile, and their Ru-II/Ru-III oxidation peaks were found at ca. +1.6 V. Hydrolysis of the binuclear [Ru-II(eta(6)-(2-phenoxyethanol))(mu(2)-Cl)Cl](2) precursor (1) resulted in binuclear hydroxido bridged species [(Ru-II(eta(6)-(2-phenoxyethanol)))(2)(mu-OH)(3)](+) and [(Ru-II(eta(6)-(2-phenoxyethanol)))(2)(mu-OH)(2)Z(2)] (Z = H2O/Cl-) in the presence of chloride ions in water. The hydrolytic behaviour of this Ru-II precursor is similar to that of the analogous species [Ru-II(eta(6)-p-cymene)(mu(2)-Cl)Cl](2) regarding the hydrolysis products and their stability constants. Formation of complexes 3 -5 by reaction of the Ru-II precursor with the (N, N) bidentate ligands was found to be relatively slow in aqueous solution. The complexation is complete already at pH 1 due to the formation of [Ru-II(eta(6)-(2-phenoxyethanol))(L)Z] complexes of significantly high stability in all cases, which are predominant species up to pH 6. However, besides the formation of the mixed hydroxido species [Ru-II(eta(6)-(2-phenoxyethanol))(L)(OH)] + at neutral and basic pH values, the slow oxidation of the RuII centre takes place as well leading to the partial loss of the arene moiety. The rate of these processes depends on the pH and its maximum was found at pH 8-9. Additionally the chlorido/aqua co-ligand exchange processes of the [Ru-II(eta(6)-(2-phenoxyethanol))(L)Cl](+) species were also monitored and only similar to 5% of the chlorido ligand was found to be replaced by water in 0.1 M chloride ion containing aqueous solutions at pH 5.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationη6-(2-phenoxyethanol) ruthenium(II)-complexes of 2,2′-bipyridine and its derivatives: Solution speciation and kinetic behaviour. Journal of Organimetallic Chemistry. ISSN 0022-0328X. Vol. 820 (2016), pp. 20-29pt_PT
dc.identifier.doi10.1016/j.jorganchem.2016.07.017pt_PT
dc.identifier.issn0022-0328X
dc.identifier.issn1872-8561
dc.identifier.urihttp://hdl.handle.net/10400.21/9558
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherElsevierpt_PT
dc.relationIF/01302/2013 - Investigator FCT Initiativept_PT
dc.relationPD103905 - Hungarian Research Foundation OTKA projectpt_PT
dc.relation.publisherversionhttps://ac.els-cdn.com/S0022328X16303084/1-s2.0-S0022328X16303084-main.pdf?_tid=4a291f54-f26c-4028-a887-8d6dff877f33&acdnat=1550752060_732c760de8d43de9ac9c0a1c9437288apt_PT
dc.subjectStability constantspt_PT
dc.subjectEquilibriapt_PT
dc.subjectRuthenium(II)-arenept_PT
dc.subjecteta(6)-(2-phenoxyethanol)pt_PT
dc.titleη6-(2-phenoxyethanol) ruthenium(II)-complexes of 2,2′-bipyridine and its derivatives: Solution speciation and kinetic behaviourpt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/5876/UID%2FQUI%2F00100%2F2013/PT
oaire.citation.endPage29pt_PT
oaire.citation.startPage20pt_PT
oaire.citation.titleJournal of Organometallic Chemistrypt_PT
oaire.citation.volume820pt_PT
oaire.fundingStream5876
person.familyNamePilon
person.familyNameRobalo
person.familyNameAnselmo Viegas Garcia
person.familyNameEnyedy
person.familyNameValente
person.givenNameAdhan
person.givenNameMaria Paula
person.givenNameMaria Helena
person.givenNameEva Anna
person.givenNameAndreia
person.identifierH-2175-­2013
person.identifier649272
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person.identifier.ciencia-idE11C-A704-9C18
person.identifier.ciencia-id5414-9AEF-4194
person.identifier.ciencia-id7C1C-E800-F13E
person.identifier.ciencia-id9F1B-8F8A-EBE6
person.identifier.orcid0000-0001-6357-1247
person.identifier.orcid0000-0002-8200-6910
person.identifier.orcid0000-0002-4344-2218
person.identifier.orcid0000-0002-8058-8128
person.identifier.orcid0000-0002-3370-208X
person.identifier.ridL-7814-2017
person.identifier.ridB-2002-2012
person.identifier.ridD-1390-2011
person.identifier.ridD-9251-2011
person.identifier.scopus-author-id57190729129
person.identifier.scopus-author-id9269662100
person.identifier.scopus-author-id6507884466
person.identifier.scopus-author-id14630434000
person.identifier.scopus-author-id23570219600
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
rcaap.rightsclosedAccesspt_PT
rcaap.typearticlept_PT
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