To avoid the problem of separation of products from catalyst in homoge
neous catalysis(1), two-phase systems have been developed in which the
catalytic complex (usually a water-soluble organometallic complex) re
mains in one (generally aqueous) phase while the products remain in a
second, immiscible phase(2). Catalysis relies on the transfer of organ
ic substrates into the aqueous catalyst phase; but the limited solubil
ity of these substrates in water leads to reaction rates much lower th
an those for conventional homogeneous catalysis. Here we show that cat
alysis at the interface of a two-phase system can be enhanced by using
a 'promoter ligand' which, although soluble in the organic phase, wil
l bind to the organometallic catalyst and thus increase its concentrat
ion dose to the interface in the aqueous phase. We demonstrate this ap
proach for the hydroformylation of 1-octene using a rhodium-based cata
lyst. A rate enhancement by a factor of 10-50 is observed when we intr
oduce the promoter ligand PPh(3) in the organic phase.