Tertiary phosphine-transition metal complexes chiral

The development of the catalytic hydrogenation system based on RhCl(PPh3)3 and methods for the resolution of optical isomers of tertiary phosphines occurred around the same time (1965), and this led to the possibility of asymmetric catalytic hydrogenation of prochiral unsaturated substances with C=C, C=0, and C=N bonds using transition metal complexes with chiral phosphine ligands. Such tertiary phosphines are of three types ... 

Primary and secondary phosphines can oxidatively add to low-valent transition metal complexes to form phosphido complexes. In contrast to phosphines, metal phosphido complexes are known to undergo fast pyramidal inversion, often on the NMR timescale. Inversion barriers for some platinum complexes, determined by NMR spectroscopy, range from 42 to 67kJmol. As a consequence, phosphido complexes containing other chiral ligands are mixtures of interconverting diastereomers. Reaction of these complexes with electrophiles yields tertiary phosphines and derivatives (Scheme 6.1). 

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