Ionic phosphine ligands with cobaltocenium backbone: Novel ligands for thehighly selective, biphasic, rhodium-catalyzed hydroformylation of 1-octenein ionic liquids

The use of electron-poor phosphine-substituted cobaltocenium salts as ligan ds for the biphasic hydroformylation in ionic liquids has been investigated . Using improved oxidation methods, 1,1'-bis(diphenylphosphino)cobaltoceniu m nitrate, 1,1'-bis(diphenylphosphino)cobaltocenium hexafluorophosphate, an d 1,1'-bis[l-methyl(1-diphenylphosphino)ethyl]cobaltocenium hexafluorophosp hate have been synthesized. 1.1'-Bis( diphenylphosphinocobaltocenium hexafl uorophosphate in particular proved to be a very suitable ligand for the bip hasic hydroformylation of 1-octene in 1-butyl-3-methylimidazolium hexafluor ophosphate (BMIM PF6), enabling high catalyst activity, high selectivity to the n-product, and no detectable catalyst leaching. In contrast to aqueous biphasic systems, the ionic liquid BMIM PF6 provides for the rhodium catal yst a low-coordinating medium with limited but sufficient solubility for 1- octene to allow high reaction rates.