All ETDs from UAB

Advisory Committee Chair

Gary Gray

Advisory Committee Members

Houston Byrd

Chris Lawson

Sadanandan Velu

Charles Watkins

Document Type


Date of Award


Degree Name by School

Doctor of Philosophy (PhD) College of Arts and Sciences


In Chapter 1, the metallacrown ethers cis-[PdCl2{Ph2P(CH2CH2O)3CH2CH2PPh2-P,P’}] and trans-PtCl2{Ph2P(CH2CH2O)3CH2CH2PPh2-P,P’} were studied. These metallacrown ethers are ideal candidates for the study of the kinetics and thermodynamics of cis-trans isomerizations because of their highly flexible backbones. We have carried out these studies using 31P NMR spectroscopy, and the equilibrium constants and thermodynamic and kinetic parameters for these reactions are reported. Chapter 2 of this dissertation explores the cation binding ability of the tartaric acid backbone proposed as the building block for the ligands developed herein for the hydroformylation of styrene. Binding studies and crystallographic analysis confirmed that incorporating the tartaric acid backbone into the proposed phosphite ligands could indeed allow for interaction of hard metal cations with the active catalyst during the hydroformylation process. Chapter 3 presents the synthesis, coordination chemistry and x-ray structural analysis of two tartaric acid-derived bis(phosphite) ligands and their transition metal complexes of molybdenum, platinum, and palladium. We found that future work would focus on functionalization of the tartaric acid backbone with substituents which contain additional donor atoms and that the functionalization would be done on the ester portion of the tartrate backbone as opposed to the hydroxy group portion. ii Chapter 4 gives the results of an in depth catalytic hydroformylation study of one ligand and the effect that hard metal cations have on the activities and selectivities of the hydroformylation process. The results show, by comparison with a known commercially available bis(phosphite) ligand, that tartaric acid derived bis(phosphite) ligands can be very active catalysts for the hydroformylation of styrene and that addition of both Li+ and Na+ had virtually no effect on the activity of the Rh(I) catalysts containing these phosphites, but instead increased the regioselectivity towards the iso product by over two-fold. In the final chapter, we report the effects of alkali metal cations on the activities, regioselectivities, and enantioselectivities in the asymmetric hydroformylation of styrene catalyzed by Rh(I) complexes of three new flexible bis(phosphite) ligands derived from tartaric acid and again compare these ligand complexes, especially to the enantioselectivities obtained, to a Rh(I) complex of Chiraphite®, one of the best commercially available bis(phosphite) ligands.



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