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Organometallic synthesis and catalysis of organotitanium and organonickel compounds and synthesis and physical chemical studies of mono, functionally substituted cyclopentadienyldicarbonyliridium compounds
Abstract
In Chapter 1 the syntheses of a series substituted $(\eta\sp5$-cyclopentadienyl)dicarbonyliridium complexes using chlorodicarbonyl(pyridine)iridium as a starting material are described, giving yields as a high as 94%. Ring substituted compounds synthesized by this route include: chloro, benzyl, pentabenzyl, acetyl, carbomethoxy, methyl, benzoyl, trimethylsilyl, cyano, N,N-dimethylamino, tetraphenyl, N,N-dimethylamino-ethyl, (tetramethyl)N,N-dimethylaminoethyl, methoxyethyl, and pentamethyl. Also examined were the effects of the ring substituent on the asymmetric and symmetric carbonyl stretching frequencies as well as the $\sp{13}$C NMR chemical shift of the carbonyl carbon. In addition the photolysis of the pentamethyl, trimethylsilyl, dimethylaminoethyl and tetramethyldimethylamino substituted cyclopentadienyl-dicarbonyliridium compounds were studied. In Chapter 2 are presented the synthesis and polymerization properties of a series of pendent amino-substituted cyclopentadienyl titanium trichloride compounds. Specifically prepared were the picolyl and diisopropylaminocyclopentadienyl, dimethylaminoethyl, pyridylethyl and diisopropylaminoethylindenyl titanium trichlorides and triisopropoxides. In addition phenylethylcyclopentadienyltrichlorotitanium was prepared. As part of the synthetic process, three new thallium reagents were prepared and characterized. Their synthetic usefulness was demonstrated by the preparation of several new organometallic compounds of rhodium, titanium, and iridium. The catalytic properties of the pendent coordinating titanium compounds were explored by polymerizing ethylene, propylene and styrene. The polymers obtained were characterized by molecular weight via viscosity measurement and GPC and tacticity via $\sp{13}$C NMR and DSC. In Chapter 3 is described a search for new late transition metal coordination and organometalic compounds which could polymerize olefins to create high molecular weight polyolefins and co-polymerize olefins and carbon monoxide to create polyketones. Specifically diimine, $o,o\sp\prime$-dimethylaminomethylphenyl, dipyridyl, and benzamidinate compounds of nickel and palladium were prepared and tested for their ability to polymerize ethylene and propylene and co-polymerize hexene or propylene and carbon monoxide. The synthesis and catalysis were only partially successful giving one molecule (R-DABNiBr$\sb2)$ that proved to be highly active for the polymerization of oefins. In addition $o,o\sp\prime$-dimethylaminomethylphenylnickel bromide appears to oligomerize both hexene-CO and propylene-CO. In connection with our search for new nickel catalysts, (diphenylphosphinylcyclopentadienylbromonickel) $\sb2$ and (diphenylphosphinylcyclopentadienylmethylnickel) $\sb2$ were prepared and characterized by NMR and X-ray crystallography. Polymer samples obtained from various polymerization runs were characterized by $\sp{13}$C NMR, GPC and DCS.
Subject Area
Organic chemistry|Chemistry|Polymers
Recommended Citation
Blais, Matthew S, "Organometallic synthesis and catalysis of organotitanium and organonickel compounds and synthesis and physical chemical studies of mono, functionally substituted cyclopentadienyldicarbonyliridium compounds" (1998). Doctoral Dissertations Available from Proquest. AAI9823720.
https://scholarworks.umass.edu/dissertations/AAI9823720