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dc.contributor.authorGómez Rubio, Manuel 
dc.contributor.authorGonzález Pérez, Juan Ignacio 
dc.contributor.authorHernández Prieto, Cristina 
dc.contributor.authorMartín Alonso, Avelino 
dc.contributor.authorMena Montoro, Miguel 
dc.contributor.authorSantamaría Angulo, Cristina 
dc.contributor.authorTemprado Morena, Manuel 
dc.date.accessioned2019-09-04T07:53:25Z
dc.date.issued2019-05-06
dc.identifier.bibliographicCitationInorganic Chemistry, 2019, v. 58, n. 9, p. 5593-5602en
dc.identifier.issn0020-1669
dc.identifier.urihttp://hdl.handle.net/10017/38889en
dc.description.abstractUse of (Me3Si)2S and [Ta(η5-C5Me5)Cl4](1) in a 4:3 ratio afforded the trimetallic sulfide cluster [Ta3(η5-C5Me5)3Cl3(μ3-Cl)(μ-S)3(μ3-S)] (2) with loss of SiClMe3. A similar reaction between 1, TaCl5, and (Me3Si)2S in a 2:1:4 ratio resulted in the analogous complex [Ta3(η5-C5Me5)2Cl4(μ3-Cl)(μ-S)3(μ3-S)] (3). Single-crystal X-ray diffraction analyses of 2 and 3 showed in all cases trinuclear tantalum sulfide clusters. On the other hand, thermal treatment of 2 with SiH3Ph generated very cleanly the dinuclear tantalum(IV) sulfide complex [Ta2(η5-C5Me5)2Cl2(μ-S)2] (4) in a quantitative way. Likewise, we found that 4 was synthesized more easily by a one-pot reaction of 1, (Me3Si)2S, and SiH3Ph in toluene. Reactions of 4 with a series of alkylating reagents rendered the dinuclear peralkylated sulfide complexes [Ta2(η5-C5Me5)2R2(μ-S)2] (R = Me 5, Et 6, CH2SiMe3 7, C3H5 8, Ph 9). Single-crystal X-ray diffraction analyses of 4, 5, and 9 showed in all cases a trans disposition of the chloro or alkyl substituents. The short Ta−Ta distances (2.918(1)−2.951(1) Å) along with DFT calculations indicate a σ-Ta− Ta interaction. Complexes 5, 6, and 8 undergo trans−cis isomerization, and mechanistic proposals are discussed based on DFT calculations.en
dc.description.sponsorshipMinisterio de Economía y Competitividad Universidad de Alcaláes_ES
dc.format.mimetypeapplication/pdfen
dc.language.isoengen
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)en
dc.rights© 2019 American Chemical Societyen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.titleMolecular Design of Cyclopentadienyl Tantalum Sulfide Complexesen
dc.typeinfo:eu-repo/semantics/articleen
dc.subject.ecienciaQuímicaes_ES
dc.subject.ecienciaChemistryen
dc.contributor.affiliationUniversidad de Alcalá. Departamento de Química Analítica, Química Física e Ingeniería Química
dc.contributor.affiliationUniversidad de Alcalá. Departamento de Química Orgánica y Química Inorgánica
dc.date.updated2019-09-04T07:52:06Z
dc.type.versioninfo:eu-repo/semantics/publishedVersionen
dc.identifier.doi10.1021/acs.inorgchem.8b03563en
dc.relation.projectIDCCG2017-EXP/036es_ES
dc.relation.projectIDinfo:eu-repo/grantAgreement/MINECO//CTQ2013-44625-R/ES/ACTIVACION Y FUNCIONALIZACION DE DINITROGENO EN COMPLEJOS POLIMETALICOS COMO ALTERNATIVA AL PROCESO HABER-BOSCH EN LA PRODUCCION DE AMONIACO/es_ES
dc.date.embargoEndDate2020-04-19
dc.rights.accessRightsinfo:eu-repo/semantics/openAccessen
dc.identifier.uxxiAR/0000030288
dc.identifier.publicationtitleInorganic Chemistryen
dc.identifier.publicationvolume58
dc.identifier.publicationlastpage5602
dc.identifier.publicationissue9
dc.identifier.publicationfirstpage5593


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