Thesis (Ph. D.)--Columbia University, 1934. / Vita. Bibliography: p. 28-30.

Thesis--Columbia University. / Cover title. Vita. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Delaware, 2006. / Principal faculty advisor: Mark A. Barteau, Dept. of Chemical Engineering. Includes bibliographical references.

Thesis (M.S.)--Florida State University, 2006. / Advisor: Marie E. Krafft, Florida State University, College of Arts and Sciences, Dept. of Chemistry and Biochemistry. Title and description from dissertation home page (viewed June 13, 2006). Document formatted into pages; contains xix, 119 pages. Includes bibliographical references.

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M.Sc. / An annual production of approximately 46 million metric tons of polyolefins worldwide, emphasizes the industrial importance of this product and the polymerisation process. Olefins are the basic building block of the petrochemical industry and are therefore readily available and cheap. Reactivity of olefins decreases from ethylene to propylene to 1-octene and makes the study of polymerisation catalysts more complex, seeing that the activity of a catalyst differs from monomer to monomer. In this study zirconocene complexes with bridged cyclopentadienyl ligands have been prepared and investigated as , possible catalysts for the polymerisation of higher aolefins. Fulvenes have been reductively coupled and used as ligands for zirconium complexes. Steric bulk of the substituents on the ligand have been increased and changes in the polymeric products have been studied. The tacticty, endgroups and chain lengths of the polyolefins have been investigated. There is currently a considerable interest in the development of 'non-metallocene' catalysts as alternatives for the polymerisation and oligomerisation of a-olefins. Chelating diamide complexes of Group 4 metals have been the focus of much attention and these compounds have shown moderate to high reactivity. However, only a few examples of the corresponding chelating alkoxides are known. In this study, alkoxide complexes of zirconium and titanium have been prepared with Schiff bases as ligands. These complexes have been evaluated as polymerisation catalysts and the products have been studied. The titanium complexes were more active than the zirconium analogues. The narrow molecular weight distribution of the polyolefins gave evidence that these catalysts are single-sited catalysts.

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It is the purpose of this paper to present experimental data for the determination of the dielectric constant and the dipole moments for a series of olefenic diesters of the cis and trans configurations.

In recent years numerous complexes have been reported in which olefins were chelated to transition metals.Ever since the generally regarded first olefin complex, Zeise's salt (32) KPt(C2H43, the interest in this field of organometallic chemistry has expanded to several families of olefinic ligands and metals like palladium(II), platinum(II) copper(I), silver(I), and more recently vanadium and titanium The nature of the bonding of olefins to metal atoms seemed to involved the interaction between pi electrons in the unsaturated molecule and the hybrid orbitals of the metal rather than a localized sigma bonds between the metal atom and a particular carbon atom. The metal was complexed to a hydrocarbon which possessed a surplus of electrons. The direct overlap of a sigma orbital of the metal anad the p-orbital of the carbon atom formed a sigma type bond. The ligand carbon atom donated a surplus bonding pi-p electrons to a vacant sigma orbital of the metal while at the same time the excess negative charge was released back to the olefin from from a pi-d orbital of the metal to an empty antibonding pi-p orbital of the carbon atom. Dewar (9) illustrated this point by molecular orbital diagram. (See figure B) [see PDF file for Formula] The metal to olefin bond consisted of two parts: (a) overlap of the pi electron density of the olefin with sigma type acceptor orbital on the metal atom and (b) a "back-bonding" resulting from the flow of electron density from filled metal dxy or other dπ - pπ hybrid orbitals into antibonding orbital on the carbon atom. A schematic diagram of platinum olefin complexes can be shown as: [see PDF file for Formula] It was the intention of this research to increase our understanding of these stable diolefin complexes. In particular, the occurrence of rearrangement upon complexation of certain ligands to most likely a more stable configuration posed an interesting project. They syntheses of diolefin complexes provided an establishment of good technique and verification of reported data. The program of study was concentrated on the complexation of cyclic diolefins with primarily palladium(II) and platinum(II) chloride.

No description available.