Abstract
Induction periods in the asymmetric hydrogenation of prochiral olefins with five-membered chelates of the type [Rh(PP)(diolefin)]BF 4 originate from the parallel-running hydrogenation of the prochiral substrate and the diolefin that enters the system as a constituent of the precatalyst. Reactivities towards the most commonly used diolefins COD or NBD can differ by three powers of ten. X-ray crystal structure analyses of [Rh(( S, S)-Et-DuPHOS)(NBD)]BF 4 and of [Rh(( R, R)-Et-DuPHOS)(COD)]BF 4 imply that a recently discussed relation between the sense of rotation of the diolefin in the precatalyst ( clockwise or anticlockwise twist) is not very likely.
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