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Acylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical study

2012Journal article Restricted access
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dc.contributor.authorAlegria, Elisabete
dc.contributor.authorSilva, Maria de Fátima Costa Guedes da
dc.contributor.authorKuznetsov, Maxim L.
dc.contributor.authorCunha, S. M. P. R. M.
dc.contributor.authorMartins, Luisa
dc.contributor.authorPombeiro, Armando
dc.date.accessioned2015-09-08T13:35:35Z
dc.date.available2015-09-08T13:35:35Z
dc.date.issued2012
dc.description.abstractTreatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl-(dppe)(2)]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R')C(O)Et (R' = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)(2)(dppe)(2)] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans[Mo(NCN)(2)(dppe)(2)], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.por
dc.identifier.citationAlegria, E. C. B. A.; [et al] – Acylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical study. Dalton Transactions. ISSN: 1477-9226. Vol. 41, nr. 45 (2012), pp. 13876-13890por
dc.identifier.doi10.1039/c2dt30867c
dc.identifier.issn1477-9226
dc.identifier.urihttp://hdl.handle.net/10400.21/5093
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherRoyal Soc Chemistrypor
dc.relationFCT- PEst-OE/QUI/UI0100/2011
dc.subjectCrystal-structurespor
dc.subjectCoordination Chemistrypor
dc.subjectStructural-Characterizationpor
dc.subjectCyanoguanidine Complexespor
dc.subjectCyanamide Complexespor
dc.subjectMetal-Complexespor
dc.subjectBond Formationpor
dc.subjectNitrilepor
dc.subjectOrganonitrilespor
dc.subjectIsomerizationpor
dc.titleAcylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical studypor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage13890por
oaire.citation.issue5por
oaire.citation.startPage13876por
oaire.citation.titleDalton Transactionspor
oaire.citation.volume41por
person.familyNameAlegria
person.familyNameKuznetsov
person.familyNameMartins
person.familyNamePombeiro
person.givenNameElisabete
person.givenNameMaxim L.
person.givenNameLuisa
person.givenNameArmando
person.identifier863202
person.identifier637885
person.identifier.ciencia-id8C1F-851A-9F1C
person.identifier.ciencia-id7018-EEFE-E023
person.identifier.ciencia-idE218-E297-A4EA
person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0003-4060-1057
person.identifier.orcid0000-0001-5729-6189
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridE-9945-2012
person.identifier.ridH-7934-2012
person.identifier.ridG-6210-2011
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id8315848300
person.identifier.scopus-author-id7102379353
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id7006067269
rcaap.rightsclosedAccesspor
rcaap.typearticlepor
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