HPNMR and in situ HPIR (HP = High Pressure) spectroscopic techniques were u
sed to study the species present in the hydroformylation of styrene by rhod
ium disphosphine systems. Rhodium precursors with BDPP [(2S,4S)-bis(dipheny
lphosphino)pentane] and CHIRAPHOS [(2R,3R)-bis(diphenylphosphino)butane] as
the chiral ligands (P-P) were used. The species observed were compared in
order to find a relation between the structures and the enantiomeric excess
es obtained for both chiral diphosphines. The effect of the P-P : [Rh] mola
r ratio and the addition of a monophosphine on the enantiomeric excess were
studied. It has been found that oxidation of the coordinated chiral diphos
phine leads to formation of rhodium species more active but less regio- and
enantio-selective.