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Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies

2016-11Journal article Restricted access
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dc.contributor.authorAlegria, Elisabete
dc.contributor.authorGuedes Da Silva, M. Fátima C.
dc.contributor.authorKuznetsov, Maxim L.
dc.contributor.authorMartins, Luisa
dc.contributor.authorPombeiro, Armando
dc.date.accessioned2017-06-05T12:00:33Z
dc.date.available2017-06-05T12:00:33Z
dc.date.issued2016-11
dc.description.abstractTreatment of trans-[Mo(NCN)(2)(dppe)(2)] with alkyl halides (RX) affords the alkylated cyanoimidocomplexes trans-[Mo(NCN)(NCNR)(dppe)(2)]X [R = Me, X = I (1); R = Et, X = I (2); R = Pr, X = I (3); R = Pr-i, X = I (4); R = CH2Ph, X = Br (5); R = CH2C6H4NO2-4, X = Br (6)], while its reaction with the trimethyloxonium salt [Me3O][BF4] affords trans-[Mo(NCN)(NCNMe)(dppe)(2)][BF4] (7). The reactions are accelerated by microwave irradiation. Complexes 1-7 were fully characterized by elemental analyses, IR and NMR spectroscopies, FAB-MS spectrometry, cyclic voltammetry and controlled potential electrolysis. The electrophilic addition to the exo-N atom of one of the cyanoimide ligands was confirmed by single crystal X-ray crystal analysis of 1. In aprotic medium and at a Pt electrode, compounds 1-7 undergo, apart from two consecutive single-electron reversible oxidations, also two successive single-electron reductions at different potentials, involving a cathodically induced trans-to-cis isomerization, following a double square ECEC-type mechanism which was studied in detail by digital simulation of the cyclic voltammograms. Quantum-chemical calculations indicate that the oxidations and reductions are mainly metal centered (although the latter with some involvement of the cyanoimide moieties), and that the reduction leads to a decrease of the relative stability of the trans isomer vs. the cis one.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationALEGRIA, Elisabete C. B. A. [et al] - Mono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studies. Electrochimica Acta. ISSN: 0013-4686. Vol. 218 (2016), pp. 252-262.pt_PT
dc.identifier.doi10.1016/j.electacta.2016.09.120pt_PT
dc.identifier.issn0013-4686
dc.identifier.urihttp://hdl.handle.net/10400.21/7148
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherElsevierpt_PT
dc.relation.publisherversionhttp://ac.els-cdn.com/S0013468616320382/1-s2.0-S0013468616320382-main.pdf?_tid=acb5819a-452b-11e7-ac32-00000aab0f27&acdnat=1496144134_1226d420a2e999fbc69f72bd157e54ddpt_PT
dc.subjectCyanoimido complexespt_PT
dc.subjectAlkylated cyanoimidopt_PT
dc.subjectDigital simulation of cyclic voltammetrypt_PT
dc.subjectElectron-transfer induced reactionspt_PT
dc.subjectDouble square ECEC-type mechanismpt_PT
dc.titleMono-alkylation of cyanoimide at a molybdenum(IV) diphosphinic center by alkyl halides: synthesis, cathodically induced isomerization and theoretical studiespt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage262pt_PT
oaire.citation.startPage252pt_PT
oaire.citation.titleElectrochimica Actapt_PT
oaire.citation.volume218pt_PT
person.familyNameAlegria
person.familyNameGuedes da Silva
person.familyNameKuznetsov
person.familyNameMartins
person.familyNamePombeiro
person.givenNameElisabete
person.givenNameM. Fátima C.
person.givenNameMaxim L.
person.givenNameLuisa
person.givenNameArmando
person.identifier863202
person.identifier789079
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person.identifier.ciencia-id7619-8E8E-979A
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.orcid0000-0003-4836-2409
person.identifier.orcid0000-0001-5729-6189
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridE-9945-2012
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person.identifier.ridH-7934-2012
person.identifier.ridG-6210-2011
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person.identifier.scopus-author-id8315848300
person.identifier.scopus-author-id6701761571
person.identifier.scopus-author-id7102379353
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id7006067269
rcaap.rightsclosedAccesspt_PT
rcaap.typearticlept_PT
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