All ETDs from UAB

Advisory Committee Chair

Gary M Gray

Advisory Committee Members

Houston Byrd

Cameron Gren

Tracy Hamilton

Aaron Lucius

Document Type

Dissertation

Date of Award

2019

Degree Name by School

Doctor of Philosophy (PhD) College of Arts and Sciences

Abstract

The synthesis and characterization of a series of novel phosphine-, phosphinite, and phosphite-functionalized transition metal complexes are reported. These compounds have applications as alkene hydroformylation catalysts. The first chapter investigates the coordination of two tartaric acid derived ligands to cis-tetracarbonylmolybdenum(0) and pentacarbonyltungsten(0) metal centers. A cis-trans equilibrium was established for the molybdenum complexes and solid-state structures were obtained for both coordination geometries. The tungsten complexes were used to determine the electronic parameters of the donor ligands. The second chapter investigates a library of ligands derived from 1,2-O-isopropylideneglycerol as catalysts for the hydroformylation of styrene. Model complexes containing molybdenum, palladium, and tungsten were synthesized and characterized by various NMR techniques. The previously published correlation between the 1JSeP and 1JWP coupling constants is also expanded. The third chapter probes the effects of unsymmetrical backbones in polyether derived ligands on the cation binding of their cis-tetracarbonylmolybdenum(0) complexes. Their syntheses have been optimized, and Rh(I) complexes of the ligands have been evaluated as catalysts for the hydroformylation of styrene in both the presence and absence of Li+ salts. These studies show that the previously hypothesized mechanism for the effect of alkali metal salt binding on hydroformylation regioselectivity may be incomplete. The final chapter outlines the use of 31P{1H} NMR in a teaching laboratory designed for undergraduates in an upper level inorganic course. Students synthesized and characterized the cis-tetracarbonylmolybdenum(0), trans-tetracarbonylmolybdenum(0), and cis-dichloropalladium(II) complexes of three phosphorus-donor ligands. These complexes were then characterized by 31P{1H} NMR and students evaluated trends in the data. Survey data shows that both knowledge of the material and students’ self-assessed confidence increased.

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