RHODIUM(I) COMPLEXES OF FERROCENYLPHOSPHINES AS EFFICIENT ASYMMETRIC CATALYSTS. THE STRUCTURE OF Fe(η5-C5H3(P(CMe3)2-1,3)(η5-C5H3(CHMeNMe2)(P(CMe3)2-1,2)

Article abstract of DOI:10.1016/0022-328X(85)87003-0

Rhodium(I) complexes of the chiral ligands Fe(η⁵-C5H5-n(P(CMe3)2)_n-1,3)(η⁵-C5H3(CHMeNMe2)P(CMe3)2-1,2 (n=0-2) are P-N bound, and are asymmetric hydrogenation catalysts.The configuration of the product from prochiral olefins is controlled by the planar chirality of the ligand.The catalyst with n=2 is the most efficient affording optical yields as good as those obtained from more conventional systems embodying PAr2 donors.Crystals of the ligand n=2 are monoclinic, P2₁, a 11.448(4), b 44.667(7), c 8.669(3) Angsroem, β 111.98(1), V 4111(2) Angstroem, Z=4 (2 molecules per asymmetric unit) D_x 1.114, D_m 1.129 g cm^-3 (by flotation in aqueous KI), final R=0.069 for 4799 observed reflections.The molecule is chiral, with an (S,S) configuration, and the two crystallographically independent molecules have almost identical geometries and conformations.The cyclopentadienyl rings are close to planar, deviate slightly from coplanarity, and are rotated by about 7 deg from an eclipsed conformation; the substituent P and C atoms are significantly displaced from the ring planes.Fe-C bond length average 2.044 and 2.092 Angstroem to unsubstituted C atoms, respectively.