Towards Bimetallic Asymmetric Hydroformylation Catalysis: Separation of the Diastereomers and Enantiomers of a Binucleating Tetraphosphine Ligand.
Date of Award
Doctor of Philosophy (PhD)
George G. Stanley
The separation of the racemic and meso diastereomers of the binucleating ligand et,ph-P4 ((Et$\rm \sb2PCH\sb2CH\sb2)(Ph)PCH\sb2P(Ph)(CH\sb2CH\sb2PEt\sb2))$ was achieved. The thiocyanate nickel(II) complexes of mixed racemic- and meso-et,ph-P4 were separated based on their different solubilities in ethanol. Cyanolysis of the separated racemic and meso nickel(II) complexes allowed the recovery of the free racemic- and meso-et,ph-P4 ligands. The many species involved in this process were identified in order to obtain consistent and improved results. After the separation of the diastereomers, the enantiomers of racemic-et,ph-P4 were separated in order to study the ability of the bimetallic chiral rhodium et,ph-P4 complexes to act as precursors of catalysts for bimetallic asymmetric hydroformylation of various vinyl esters.
Alburquerque, Pia Rosario, "Towards Bimetallic Asymmetric Hydroformylation Catalysis: Separation of the Diastereomers and Enantiomers of a Binucleating Tetraphosphine Ligand." (1997). LSU Historical Dissertations and Theses. 6408.