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How do nitriles compare with isoelectronic alkynyl groups in the electronic communication between iron centers bridged by phenylenebis-and-tris(nitrile) ligands? An electronic and crystal-structure study

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dc.contributor.authorBonniard, Lauréline
dc.contributor.authorKahlal, Samia
dc.contributor.authorDiallo, Abdou K.
dc.contributor.authorOrnelas, Cátia
dc.contributor.authorRoisnel, Thierry
dc.contributor.authorManca, Gabriele
dc.contributor.authorRodrigues, João
dc.contributor.authorRuiz, Jaime
dc.contributor.authorAstruc, Didier
dc.contributor.authorSaillard, Jean-Yves
dc.date.accessioned2019-06-19T09:05:34Z
dc.date.available2019-06-19T09:05:34Z
dc.date.issued2011
dc.description.abstractDensity functional theory (DFT) calculations on the model [{FeCp(dpe)}(2){1,4-C(6)H(4)(CN)(2)}](2+) (3(2+); dpe = diphosphinoethane) of salts of the cations [{FeCp(dppe)}(2){1,4-C(6)H(4)(CN)(2)}](2+) (1(2+); dppe = 1,2-bis[diphenyldiphosphino]ethane) and [{FeCp*(CO)(2)}(2){1,4-C(6)H(4)(CN)(2)}](2+) (2(2+)), for which the X-ray crystal structures have been determined, as well as on its isomer [{FeCp(dpe)}(2){1,3-C(6)H(4)(CN)(2)}](2+) (4(2+)) and on the related complex [{FeCp(dpe)}(3){1,3,5-C(6)H(3)(CN)(3)}](3+) (5(2+)), indicate that the highest occupied molecular orbitals (HOMOs) of these compounds are localized on the metal centers with negligible participation of the C(6) ring. Thus, the poly(nitrile)phenylene ligand efficiently quenches the electronic communication between the metal centers. This is at variance with the related isoelectronic polyacetylene phenylene complexes, in which the iron centers have been shown to be electronically coupled. Consistently, apart from the case of 3(3+), which shows some degree of delocalization, all of the oxidized forms of 3(2+), 4(2+), and 5(2+) can be described as class II, localized mixed-valent species, in agreement with the electrochemical data showing two close oxidation potentials around 1 V vs FeCp*(2). This is at variance with the p-phenylene-bridged biethynyldiiron analogue, for which extended electronic delocalization was earlier shown to provide greater degree of delocalization of the mixed valency. Time-dependent DFT calculations on 3(2+), 4(2+), and 5(2+) indicate that the lowest-energy absorption band is associated with metal-to-ligand charge-transfer transitions involving the metallic HOMOs and the two lowest unoccupied molecular orbitals that derive from the lowest π*(phenylene) orbitals with some π*(CN) bonding admixture.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationBonniard, L., Kahlal, S., Diallo, A. K., Ornelas, C., Roisnel, T., Manca, G., ... & Saillard, J. Y. (2010). How Do Nitriles Compare with Isoelectronic Alkynyl Groups in the Electronic Communication between Iron Centers Bridged by Phenylenebis-and-tris (nitrile) Ligands? An Electronic and Crystal-Structure Study. Inorganic chemistry, 50(1), 114-124.pt_PT
dc.identifier.doi10.1021/ic101415cpt_PT
dc.identifier.issn0020-1669
dc.identifier.urihttp://hdl.handle.net/10400.13/2407
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherAmerican Chemical Societypt_PT
dc.subjectNitrilespt_PT
dc.subjectIsoelectronic Alkynyl Groupspt_PT
dc.subjectElectronic Communication between Iron Centers Bridged by Phenylenebis-and-tris(nitrile) Ligandspt_PT
dc.subjectElectronic and Crystal-Structure Studypt_PT
dc.subject.pt_PT
dc.subjectFaculdade de Ciências Exatas e da Engenhariapt_PT
dc.subjectCentro de Química da Madeira
dc.titleHow do nitriles compare with isoelectronic alkynyl groups in the electronic communication between iron centers bridged by phenylenebis-and-tris(nitrile) ligands? An electronic and crystal-structure studypt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage124pt_PT
oaire.citation.startPage114pt_PT
oaire.citation.titleInorganic Chemistrypt_PT
oaire.citation.volume50(1)pt_PT
person.familyNameCapelo Ornelas Megiatto
person.familyNameRodrigues
person.givenNameCatia Cristina
person.givenNameJoão
person.identifier.ciencia-id6019-09BE-69C1
person.identifier.ciencia-idA81C-620E-DD6A
person.identifier.orcid0000-0001-8020-9776
person.identifier.orcid0000-0003-4552-1953
person.identifier.ridB-6816-2008
person.identifier.scopus-author-id9233278800
rcaap.rightsrestrictedAccesspt_PT
rcaap.typearticlept_PT
relation.isAuthorOfPublication614733a3-d90f-4bfa-8edd-6d07cecd680f
relation.isAuthorOfPublication53031fca-b2e7-4ce4-bda9-61e486da4547
relation.isAuthorOfPublication.latestForDiscovery53031fca-b2e7-4ce4-bda9-61e486da4547

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