dc.contributor.author | Gómez Rubio, Manuel | |
dc.contributor.author | González Pérez, Juan Ignacio | |
dc.contributor.author | Hernández Prieto, Cristina | |
dc.contributor.author | Martín Alonso, Avelino | |
dc.contributor.author | Mena Montoro, Miguel | |
dc.contributor.author | Santamaría Angulo, Cristina | |
dc.contributor.author | Temprado Morena, Manuel | |
dc.date.accessioned | 2019-09-04T07:53:25Z | |
dc.date.issued | 2019-05-06 | |
dc.identifier.bibliographicCitation | Inorganic Chemistry, 2019, v. 58, n. 9, p. 5593-5602 | en |
dc.identifier.issn | 0020-1669 | |
dc.identifier.uri | http://hdl.handle.net/10017/38889 | en |
dc.description.abstract | Use 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.sponsorship | Ministerio de Economía y Competitividad
Universidad de Alcalá | es_ES |
dc.format.mimetype | application/pdf | en |
dc.language.iso | eng | en |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) | en |
dc.rights | © 2019 American Chemical Society | en |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | en |
dc.title | Molecular Design of Cyclopentadienyl Tantalum Sulfide Complexes | en |
dc.type | info:eu-repo/semantics/article | en |
dc.subject.eciencia | Química | es_ES |
dc.subject.eciencia | Chemistry | en |
dc.contributor.affiliation | Universidad de Alcalá. Departamento de Química Analítica, Química Física e Ingeniería Química | |
dc.contributor.affiliation | Universidad de Alcalá. Departamento de Química Orgánica y Química Inorgánica | |
dc.date.updated | 2019-09-04T07:52:06Z | |
dc.type.version | info:eu-repo/semantics/publishedVersion | en |
dc.identifier.doi | 10.1021/acs.inorgchem.8b03563 | en |
dc.relation.projectID | CCG2017-EXP/036 | es_ES |
dc.relation.projectID | info: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.embargoEndDate | 2020-04-19 | |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | en |
dc.identifier.uxxi | AR/0000030288 | |
dc.identifier.publicationtitle | Inorganic Chemistry | en |
dc.identifier.publicationvolume | 58 | |
dc.identifier.publicationlastpage | 5602 | |
dc.identifier.publicationissue | 9 | |
dc.identifier.publicationfirstpage | 5593 | |