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Hydride Mobility in Trinuclear Sulfido Clusters with the Core [Rh 3 (μ‐H)(μ 3 ‐S) 2 ]: Molecular Models for Hydrogen Migration on Metal Sulfide Hydrotreating Catalysts
Author(s) -
Jiménez M. Victoria,
Lahoz Fernando J.,
Lukešová Lenka,
Miranda José R.,
Modrego Francisco J.,
Nguyen Duc H.,
Oro Luis A.,
PérezTorrente Jesús J.
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201100138
Subject(s) - chemistry , hydride , norbornadiene , ligand (biochemistry) , deprotonation , stereochemistry , cluster (spacecraft) , crystallography , catalysis , bridging ligand , medicinal chemistry , metal , crystal structure , organic chemistry , ion , biochemistry , receptor , computer science , programming language
The treatment of [{Rh(μ‐SH){P(OPh) 3 } 2 } 2 ] with [{M(μ‐Cl)(diolef)} 2 ] (diolef=diolefin) in the presence of NEt 3 affords the hydrido–sulfido clusters [Rh 3 (μ‐H)(μ 3 ‐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 [Rh 2 Ir(μ‐H)(μ 3 ‐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 [RhIr 2 (μ‐H)(μ 3 ‐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)(PPh 3 )} 2 ] by [M(acac)(diolef)] (acac=acetylacetonate) results in the formation of hydrido–sulfido clusters [Rh 3 (μ‐H)(μ 3 ‐S) 2 (CO) 2 (diolef)(PPh 3 ) 2 ] (diolef=cod for 6 , nbd for 7 ) and [Rh 2 Ir(μ‐H)(μ 3 ‐S) 2 (CO) 2 (cod)(PPh 3 ) 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 PPh 3 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.