| Notes: | Advisor: Richard F. Jordan.
Thesis (Ph.D.)--The University of Chicago, Division of the Physical Sciences, Department of Chemistry, 2011.
Dissertation Abstracts International, Volume: 73-04, Section: B, page: .
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| Summary: | The objective of this thesis is to develop a [PO]Pd catalyst ([PO] = generic phosphinearenesulfonate ligand) that exhibits high activity and stability, produces polymers with high molecular weight, and incorporates high levels of vinyl ethers in ethylene/alkyl-vinyl-ether copolymerizations, and to probe the factors that govern these properties.
Chapter 1 is an introduction to [PO]Pd olefin polymerization catalysts. Chapter 2 describes the synthesis of a new, moderately bulky phosphine-arenesulfonate ligand, 2-{(2-methoxyphenyl)-(2',6'-dimethoxy-2-biphenyl)phosphine}-4-methylbenzenesulfonate ([POOMeBP]) and palladium complexes of this ligand. Chapter 3 describes the ethylene homopolymerization and ethylene/alkyl-vinyl-ether copolymerization behavior of [POOMeBP] PdMeL catalysts and comparative studies of [PO-OMe]PdMeL catalysts. These results provide insight into the factors that control catalyst stability and polymer properties.
Chapter 4 describes the carbonylation of various [PO]PdMe species. Different base-free alkyl- and arylphophino-arenesulfonate [PO]PdMe species were prepared in order to probe the differences in the CO coordination and insertion behavior, and to gain insight into the influence of the [PO] ligand on the electronic character of the palladium center.
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