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Título

Novel gem-dithiolato-bridged rhodium hydroformylation catalysts: Bridging the gap in dinuclear rhodium thiolate chemistry

AutorHernandez-Gruel, Marc A. F.; Gracia-Arruego, Gustavo; Rivas, Angel B.; Dobrinovich, Isabel T.; Lahoz, Fernando J. ; Pardey, Alvaro J.; Oro, Luis A. ; Pérez-Torrente, Jesús J.
Palabras claveRhodium
gem-Dithiolato ligands
Dinuclear complexes
Hydroformylation
Homogeneous catalysis
Fecha de publicación2007
EditorWiley-VCH
CitaciónEuropean Journal of Inorganic Chemistry (36): 5677-5683 (2007)
ResumenThe direct protonation of the bridging hydroxo ligands in [Rh(μ-OH)(cod)]2 by 1,1-dimercaptocyclohexane [Chxn(SH) 2] yields the gem-dithiolato-bridged compound [Rh2(μ- S2Chxn)-(cod)2] (1). The dinuclear framework in 1 is supported by a 1,1-cyclohexanedithiolato ligand exhibiting a 1:2κ2S,1:2κ2S′ coordination mode. Compound 1 is an active catalyst precursor in the presence of P-donor ligands for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature (100 PSI, 353 K). The best results were obtained with phosphite ligands as modifying ligands. An aldehyde selectivity of 97 %, a regioselectivity towards the linear aldehyde of 81 %, and turnover frequencies of up to 198 h-1 were obtained with the catalytic system 1/P(OMe)3. The dinuclear compound [Rh2(μ-S 2Chxn)(CO)2(PPh3)2] (2) was isolated from the catalytic solutions resulting from the system 1/PPh3 and was characterized by spectroscopic means and by X-ray diffraction to be the frans isomer. The mixed-ligand dinuclear complexes 2 and [Rh2(μ- S2Chxn)(CO)2(PCy3)2] (3) (Cy = cyclohexyl) were independently prepared by reaction of Chxn(SH)2 with the mononuclear complexes [Rh(acac)(CO)-(PR3)] in the appropriate molar ratio.
Versión del editorhttp://dx.doi.org/10.1002/ejic.200700756
URIhttp://hdl.handle.net/10261/133802
DOI10.1002/ejic.200700756
Identificadoresdoi: 10.1002/ejic.200700756
issn: 1434-1948
e-issn: 1099-0682
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