Molecular Design of Cyclopentadienyl Tantalum Sulfide Complexes
Authors
Gómez Rubio, Manuel; González Pérez, Juan Ignacio; Hernández Prieto, Cristina; Martín Alonso, Avelino; Mena Montoro, Miguel; [et al.]Identifiers
Permanent link (URI): http://hdl.handle.net/10017/38889DOI: 10.1021/acs.inorgchem.8b03563
ISSN: 0020-1669
Date
2019-05-06Embargo end date
2020-04-19Affiliation
Universidad de Alcalá. Departamento de Química Analítica, Química Física e Ingeniería Química; Universidad de Alcalá. Departamento de Química Orgánica y Química InorgánicaFunders
Ministerio de Economía y Competitividad
Universidad de Alcalá
Bibliographic citation
Inorganic Chemistry, 2019, v. 58, n. 9, p. 5593-5602
Project
CCG2017-EXP/036
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/
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Rights
Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
© 2019 American Chemical Society
Access rights
info:eu-repo/semantics/openAccess
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.
Files in this item
Files | Size | Format |
|
---|---|---|---|
Molecular_Gomez_InorgChem_2019.pdf | 1.361Mb |
|
Files | Size | Format |
|
---|---|---|---|
Molecular_Gomez_InorgChem_2019.pdf | 1.361Mb |
|
Collections
- QUIMINOR - Artículos [235]