Fan-chou Xu

Date of Award


Degree Type


Degree Name

Doctor of Philosophy


The homogeneous, asymmetric hydrosilylation of prochiral ketones using chiral Rh catalysts of the amphos, P-N, and diamphos, P-N-N, chelate ligands was studied in both solution and the solid state using X-ray crystallographic and spectroscopic techniques, including {dollar}\sp1{dollar}H and {dollar}\sp{lcub}31{rcub}{dollar}P NMR, Visible, Infra Red, and Mass Spectroscopy. These studies provided a basis for relating the catalyst shape to the optical yield, and allowed the elucidation of a mechanistic scheme for homogeneous asymmetric hydrosilylation. In a certain favourable case, an oxidative addition produce RhHCl(SiCl{dollar}\sb3{dollar})(PPh{dollar}\sb3)\sb2{dollar} was isolated and characterized by a single crystal X-ray diffraction study.;In tests for the hydrosilylation of prochiral ketones using a new and bulky {dollar}\alpha{dollar}-naphthylphenyldihydrosilane as the silane reagent with the Rh-(P-N) complexes as the catalysts, very high chemical yields (80%-95%), fairly high optical yields of the alcohol (up to 57%), and relatively low optical yields of only the ({dollar}S{dollar})-configuration of the ({dollar}-{dollar})-{dollar}\alpha{dollar}-NpPhMeSi*H silane were obtained.



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