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New Ligands for Rh‐Catalysed Hydroformylation of 1‐Octene in Supercritical Carbon Dioxide – X‐ray Structure of [Rh{PPh 2 (OC 9 H 19 )} 4 ]PF 6
Author(s) -
GiménezPedrós Marta,
Aghmiz Ali,
Ruiz Núria,
MasdeuBultó Anna M.
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500790
Subject(s) - hydroformylation , chemistry , toluene , supercritical carbon dioxide , catalysis , alkyl , medicinal chemistry , supercritical fluid , rhodium , ligand (biochemistry) , organic chemistry , biochemistry , receptor
The new P‐donor ligands PPh 3– n (OC 9 H 19 ) n ( n = 3, 2, 1) containing branched alkyl chains were synthesised and their coordination to Rh I and Pd II studied. The X‐ray structure of [Rh{PPh 2 (OC 9 H 19 )} 4 ]PF 6 was determined. Reaction of the [Rh(acac)(CO) 2 ]/PPh 3– n (OC 9 H 19 ) n systems with CO/H 2 at 5 atm and 80 °C in toluene led to the formation of [RhH(CO){PPh 3– n (OC 9 H 19 ) n } 3 ] as the main species. The Rh‐catalysed hydroformylation of 1‐octene with these ligands was investigated in supercritical carbon dioxide (scCO 2 ) and toluene as solvents. Although the catalytic systems are not soluble in scCO 2 , they are active. The activities are higher in toluene than in scCO 2 but the selectivities for aldehydes in the case of the phosphonite derivative are higher in the supercritical medium than in toluene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)