Rhodium(I) and (III) Complexes of Some Phospholes and Their Behavior as Homogeneous Hydrogenation Catalysts

1972 ◽  
Vol 50 (22) ◽  
pp. 3714-3718 ◽  
Author(s):  
David G. Holah ◽  
Alan N. Hughes ◽  
Benjamin C. Hui
Keyword(s):  
Homogeneous Hydrogenation ◽  
Homogeneous Catalysts ◽  
Hydrogenation Catalysts ◽  
Chloride Hydrate

Reactions between rhodium(III) chloride hydrate and certain phospholes are described; these result in the formation of both Rh (III) and Rh (I) complexes. The phospholes also react with Rh (I) carbonyl and ethylene complexes. The products of these reactions were investigated as homogeneous catalysts in the hydrogenation of 1-hexene, and some show relative rates of hydrogenation comparable with that of hydridocarbonyltris(triphenylphosphine)rhodium(I) but slower than that of tris(triphenylphosphine)rhodium (I) chloride.

Rhodium(I) complexes of β-diketonates and related ligands as homogeneous hydrogenation catalysts

1991 ◽  
Vol 66 (3) ◽  
pp. 251-269 ◽  
Author(s):  
William R. Cullen ◽  
Steven J. Rettig ◽  
Eugene B. Wickenheiser
Keyword(s):  
Homogeneous Hydrogenation ◽  
Hydrogenation Catalysts

KINETIC STUDIES OF CHLORO COMPLEXES OF RHODIUM AS HYDROGENATION CATALYSTS

1966 ◽  
Vol 44 (2) ◽  
pp. 233-242 ◽  
Author(s):  
B. R. James ◽  
G. L. Rempel
Keyword(s):  
Maleic Acid ◽  
Kinetic Studies ◽  
Homogeneous Catalyst ◽  
Ferric Ion ◽  
Homogeneous Hydrogenation ◽  
Acid Complex ◽  
Olefinic Bond ◽  
Hydrogenation Catalysts ◽  
Chloro Complexes ◽  
Anionic Complexes

The anionic complexes [RhCl6]3−, [Rh(H2O)Cl5]2−, and [Rh(H2O)2Cl4]− activate molecular hydrogen for the reduction of ferric ion in aqueous acid solution; the catalytic activity increased with increasing number of chloride ligands present. Cationic and neutral chloroaquorhodium(III) complexes did not homogeneously catalyze the reduction of ferric ion, the complexes themselves being reduced to metallic rhodium, a powerful heterogeneous catalyst.Chloro complexes of rhodium(III) and rhodium(I) were not effective catalysts in aqueous solution for the homogeneous hydrogenation of the olefinic bond in maleic acid. Anionic chlororhodate(III) complexes were reduced by hydrogen to the univalent state, this state being stabilized against further reduction to the metal by complexing with the maleic acid present. Preliminary studies indicate that in dimethylacetamide solution rhodium (III) trichloride is an effective homogeneous catalyst for the reduction of maleic acid to succinic acid by hydrogen, the reaction proceeding through a rhodium (I) – maleic acid complex.

scholarly journals Abbau von Induktionsperioden und Steigerung der Aktivität homogener Hydrierungskatalysatoren mit Iridium als Zentralatom / Reduction of Induction Periods and Increase of Activity of Homogenous Iridium Hydrogenation Catalysts

1978 ◽  
Vol 33 (9) ◽  
pp. 997-1000 ◽  
Author(s):  
Erich Hitzel
Keyword(s):  
Induction Period ◽  
Homogeneous Hydrogenation ◽  
Hydrogenation Catalysts ◽  
Induction Periods

With complexes of iridium as catalysts, induction periods are typical for homogeneous hydrogenation of olefins in bulk. The induction period decreases, as a rule with increasing activity, at higher temperatures and may be suppressed with dibenzoylperoxide, azobisisobutyrodinitrile, tetrachloro-1,4-benzoquinone or by preactivation. Triethylamin and SnCl2 · 2H2O are unsuitable additives. The operation “preactivation” leads additionally to great substrate/catalyst-turnover numbers.

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