Abstract
In this paper, we report on novel Rh/phosphonate−phosphine catalysts for the aqueous two-phase hydroformylation of long-chain olefins. The amphiphilic ligands Ph2P−(CH2)10−PO3Na2 and Ph2P−(CH2)12−PO3Na2 have been shown to form Rh catalysts that are superior to Rh/TPPTS systems. Aldehyde selectivities higher than 95% and high activities (e.g., TOF of 660 h-1 at 88% yield) were achieved. Counterions such as Na+, K+, NH4+, and NH3Pr+ influence the catalyst retention, whereas the lowest rhodium losses into the organic phase were found with a sodium phosphonate ligand. Phase separation by simple decantation was accelerated when methanol was added to the biphasic system.
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