English   español  
Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/52833
Share/Impact:
Statistics
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar a otros formatos:

Title

Hydride mobility in trinuclear sulfido clusters with the core [Rh 3(μ-H)(μ3-S)2]: Molecular models for hydrogen migration on metal sulfide hydrotreating catalysts

AuthorsJiménez, M. Victoria ; Lahoz, Fernando J. ; Lukešová, Lenka; Miranda, J. R.; Modrego, Francisco J. ; Nguyen, Duc H.; Oro, Luis A. ; Pérez-Torrente, Jesús J.
Issue Date2011
PublisherWiley-VCH
CitationChemistry - A European Journal 17(29): 8115-8128 (2011)
AbstractThe treatment of [{Rh(μ-SH){P(OPh)3}2} 2] with [{M(μ-Cl)(diolef)}2] (diolef=diolefin) in the presence of NEt3 affords the hydrido-sulfido clusters [Rh 3(μ-H)(μ3-S)2(diolef){P(OPh) 3}4] (diolef=1,5-cyclooctadiene (cod) for 1, 2,5-norbornadiene (nbd) for 2, and tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5, 7-triene (tfb) for 3) and [Rh2Ir(μ-H)(μ3-S) 2(cod){P(OPh)3}4] (4). Cluster 1 can be also obtained by treating [{Rh(μ-SH){P(OPh)3}2}2] with [{Rh(μ-OMe)(cod)}2], although the main product of the reaction with [{Ir(μ-OMe)(cod)}2] was [RhIr2(μ-H) (μ3-S)2(cod)2{P(OPh)3} 2] (5). The molecular structures of clusters 1 and 4 have been determined by X-ray diffraction methods. The deprotonation of a hydrosulfido ligand in [{Rh(μ-SH)(CO)(PPh3)}2] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido-sulfido clusters [Rh3(μ-H)(μ3-S)2(CO)2(diolef) (PPh3)2] (diolef=cod for 6, nbd for 7) and [Rh 2Ir(μ-H)(μ3-S)2(CO)2(cod) (PPh3)2] (8). Clusters 1-3 and 5 exist in solution as two interconverting isomers with the bridging hydride ligand at different edges. Cluster 8 exists as three isomers that arise from the disposition of the PPh3 ligands in the cluster (cis and trans) and the location of the hydride ligand. The dynamic behaviour of clusters with bulky triphenylphosphite ligands, which involves hydrogen migration from rhodium to sulfur with a switch from hydride to proton character, is significant to understand hydrogen diffusion on the surface of metal sulfide hydrotreating catalysts.
Publisher version (URL)http://dx.doi.org/10.1002/chem.201100138
URIhttp://hdl.handle.net/10261/52833
DOI10.1002/chem.201100138
Identifiersissn: 0947-6539
e-issn: 1521-3765
Appears in Collections:(ISQCH) Artículos
(ICMA) Artículos
Files in This Item:
File Description SizeFormat 
Hydrotreating Catalysts.pdf4,23 MBAdobe PDFThumbnail
View/Open
Show full item record
Review this work
 

Related articles:


WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.