No description available.

During the course of this work we have synthesized and evaluated a series of new enantiopure silyl triflmides as catalysts for asymmetric reactions. 3-Phenyl dialkylsilyl ketones, which were the key precursors to the target silyl triflmides were prepared by 1,4-addition of the corresponding silyl cuprate to enones, and resolved by chiral HPLC. Enantiopure trans silyl ketones were successfully reduced via the corresponding tosylhydrazones by the NaBH3CN/ZnCl2 system. However, due to an isomerization of the tosylhydrazone during the reaction, cis isomers (m = 0) were reduced via the corresponding dithioketals followed by desulfurization. The diastereoselective synthesis of enantiopure silyl triflimides from enantiomerically pure compounds has been also studied. The enantiopure trialkylsilyl triflimides were generated in situ by protodesilylation of the corresponding phenylsilanes with bis-(trifluoromethylsulfonyl)imide. The Diels-Alder reaction of methyl acrylate with cyclopentadiene was used as the model reaction for testing the new chiral catalysts : 1) Almost all silyl triflimides were efficient catalysts giving high yields and excellent diastereoselectivities in favour of the endo-isomer. 2) the best ee's (up to 56%) were obtained from catalysts carrying an aryl group directly attached to the cyclohexane ring (m = 0) which were much better than those obtained from catalysts carrying a benzyl-type group (m = 1). Interestingly catalysts of the same configuration carrying phenyl or naphthyl group gave cycloadducts of opposite configuration. 3) When m = 0, additional substituents at position-3 or 6 of the cyclohexyl ring had little influence on the ee. However, for m = 1, a methyl group at C2 increased the ee from 3% to 35%. 4) The replacement of the methyl groups connected to the silicon atom by bulkier ethyl groups decreased the ee (m = 0). 5) When m = 0, ee's for cycloaddition reactions of N,N-dimethyl acrylamide or acryloxazolidinone with cyclopentadiene were lower than those obtained with methyl acrylate.

This doctoral dissertation described herein will be comprised of two parts. The first portion will address our efforts towards the synthesis of [alpha]-amino carbonyls from silyl enol ethers and the second portion will describe our unrelated efforts towards the synthesis of proaporphine alkaloids. A full discussion of the relevant literature, experiments and development of the methodologies will be provided along with all relevant experimental data. Part I: The [alpha]-amino carbonyl moiety has great potential for being a very useful synthetic intermediate for the incorporation of nitrogen owing to the synthetic utility and versatility of the carbonyl functional group. Despite this potential the synthesis has long been problematic owing to their tendency to undergo condensation reactions. We aimed to synthesize them utilizing a protected carbonyl in the form of a triisopropylsilyl enol ether and an electrophilic nitrogen source that could incorporate the nitrogen via an ene-[2,3] sigmatropic reaction sequence. To this end we used an N-sulfinyl carbamate as an electrophilic source of nitrogen that could be utilized for a regiospecific allylic amination of alkenes or could be used to form a highly reactive sulfur diimide that could be used for the allylic amination of alkenes or silyl enol ethers. Part II: Many pharmacologically important and synthetically interesting alkaloids have been formed in nature by the o,p oxidative phenolic coupling of various benzyl-tetrahydroisoquinoline alkaloids. One major class of alkaloids derived from this generalized oxidation is the proaporphine alkaloids and they possess an acid labile spirocyclic-dienone system obtained from this coupling. These compounds have great potential for being used for their anesthetic properties. Despite the relative ease of synthesizing the benzylisoquinoline alkaloids the application of the biomimetic oxidative coupling to make the quaternary center of these compounds gives very poor yields. We opted to form this spiro-dienone system by using a two step Suzuki coupling-para phenolate alkylation methodology that had been used to synthesize the related alkaloids codeine and narwedeine. In doing this we opted to extend the practical application of this methodology by the displacement of an alcohol derived leaving group. / text

No description available.

No description available.

The solid state structures and the physical, solution magnetic, solid state magnetic, and spectroscopic (NMR and UV/Vis) properties of a range of oxygen- and nitrogen-free dialkylmanganese(II) complexes are reported, and the solution reactivity of these complexes towards H2 and ZnEt2 is described. The dialkyl compounds investigated are [{Mn(μ-CH2SiMe3)2}∞] (1), [{Mn(CH2CMe3)(μ-CH2CMe3)2}2{Mn(μ-CH2CMe3)2Mn}] (2), [Mn(CH2SiMe3)2(dmpe)] (3) (dmpe = 1,2-bis(dimethylphosphino)ethane), [{Mn(CH2CMe3)2(μ-dmpe)}2] (4), [{Mn(CH2SiMe3)(μ-CH2SiMe3)}2(μ-dmpe)] (5), [{Mn(CH2CMe3)(μ-CH2CMe3)}2(μ-dmpe)] (6), [{Mn(CH2SiMe3)(μ-CH2SiMe3)}2(μ-dmpm)] (7) (dmpm = bis(dimethylphosphino)methane), and [{Mn(CH2CMe3)(μ-CH2CMe3)}2(μ-dmpm)] (8). Syntheses for 1-4 have previously been published, but the solid state structures and most properties of 2-4 had not been described. Compounds 5 and 6, with a 1:2 dmpe:Mn ratio, were prepared by reaction of 3 and 4 with base-free 1 and 2, respectively. Compounds 7 and 8 were accessed by reaction of 1 and 2 with 0.5 or more equivalents of dmpm per manganese atom. An X-ray structure of 2 revealed a tetrametallic structure with two terminal and six bridging alkyl groups. In the solid state, bis(phosphine)-coordinated 3-8 adopted three distinct structural types: (a) monometallic [LMnR2], (b) dimetallic [R2Mn(μ-L)2MnR2], and (c) dimetallic [{RMn(μ-R)}2(μ-L)] (L = dmpe or dmpm). Compound 3 exhibited particularly desirable properties for an ALD or CVD precursor, melting at 62-63 °C, subliming at 60 °C (5 mTorr), and showing negligible decomposition after 24 h at 120 °C. Comparison of variable temperature solution and solid state magnetic data provided insight into the solution structures of 2-8. Solution reactions of 1-8 with H2 yielded manganese metal, demonstrating the thermodynamic feasibility of the key reaction steps required for manganese(II) dialkyl complexes to serve, in combination with H2, as precursors for metal ALD or pulsed-CVD. By contrast, the solution reactions of 1-8 with ZnEt2 yielded a zinc-manganese alloy with an approximate 1:1 Zn:Mn ratio. Wilkinson’s manganese(I) ethylene hydride complex trans-[(dmpe)2MnH(C2H4)] (10) can react as a source of a low-coordinate manganese(I) ethyl complex. This is illustrated in the reactivity of 10 towards a variety of reagents in this work (vide infra). The proposed low-coordinate intermediate, [(dmpe)2MnEt] (13), was not observed spectroscopically, but could be trapped using isonitrile ligands; reaction of 10 with CNR (R = tBu, o-xylyl) afforded the manganese(I) ethyl complexes [(dmpe)2MnEt(CNR)] (14a: R = tBu, 14b: R = o-xylyl). Ethyl complex 14a did not react further with CNtBu at 80 °C. By contrast, complex 14b reacted with excess o-xylyl isonitrile to form 1,1 insertion products, including the iminoacyl complex [(dmpe)Mn(CNXyl)3{C(=NXyl)CEt(=NXyl)}] (15, Xyl = o-xylyl). Complexes 14a-b and 15, as well as previously reported 10, were crystallographically characterized, and DFT calculations were employed to probe the accessibility of cis ethylene hydride and ethyl isomers of 10. Reaction of the ethylene hydride complex trans-[(dmpe)2MnH(C2H4)] (10) with H2SiEt2 at 20 °C afforded the silylene hydride [(dmpe)2MnH(=SiEt2)] (16Et2) as the trans isomer. By contrast, reaction of 10 with H2SiPh2 at 60 °C afforded [(dmpe)2MnH(=SiPh2)] (16Ph2) as a mixture of the cis (major) and trans (minor) isomers, featuring a Mn–H–Si interaction in the former. The reaction to form 16Ph2 also yielded [(dmpe)2MnH2(SiHPh2)] (18Ph2); [(dmpe)2MnH2(SiHR2)] {R = Et (18Et2) and Ph (18Ph2)} were accessed cleanly by reaction of 16R2 with H2. Both 16Et2 and 16Ph2 engaged in unique reactivity with ethylene, generating the silene hydride complexes cis-[(dmpe)2MnH(R2Si=CHMe)] {R = Et (19Et2) and Ph (19Ph2)}. Compounds trans-16Et2, cis-16Ph2, and 19Ph2 were crystallographically characterized, and bonding in 16Et2 and 19Et2 was probed computationally. trans-[(dmpe)2MnH(C2H4)] (10) reacted with primary hydrosilanes H3SiR (R = Ph, nBu) at 60 °C to afford ethane and the manganese disilyl hydride complexes [(dmpe)2MnH(SiH2R)2] (20Ph: R = Ph, 20Bu: R = nBu). 20R reacted with ethylene to form silene hydride complexes [(dmpe)2MnH(RHSi=CHMe)] (19Ph,H: R = Ph, 19Bu,H: R = nBu). Compounds 19R,H reacted with a second equivalent of ethylene to generate [(dmpe)2MnH(REtSi=CHMe)] (19Ph,Et: R = Ph, 19Bu,Et: R = nBu), resulting from apparent ethylene insertion into the silene Si–H bond. Furthermore, in the absence of ethylene, silene complex 19Bu,H slowly isomerized to the silylene hydride complex [(dmpe)2MnH(=SiEtnBu)] (16Bu,Et). Reactions of 20R with ethylene likely proceed via low-coordinate silyl {[(dmpe)2Mn(SiH2R)] (17Ph: R = Ph, 17Bu: R = nBu)} or silylene-hydride {[(dmpe)2MnH(=SiHR)] (16Ph,H: R = Ph, 16Bu,H: R = nBu)} intermediates accessed from 20R by H3SiR elimination. DFT calculations and high temperature NMR spectra support the accessibility of these intermediates, and reactions of 20R with isonitriles or N-heterocyclic carbenes yielded the silyl isonitrile complexes [(dmpe)2Mn(SiH2R)(CNR')] (21a-d: R = Ph or nBu; R' = o-xylyl or tBu), and NHC-stabilized silylene-hydride complexes [(dmpe)2MnH{=SiHR(NHC)}] (22a-d: R = Ph or nBu; NHC = 1,3-diisopropylimidazolin-2-ylidene or 1,3,4,5-tetramethyl-4-imidazolin-2-ylidene), respectively, all of which were crystallographically characterized. Manganese silyl dihydride complexes [(dmpe)2MnH2(SiHR2)] {R = Ph (18Ph2) or Et (18Et2)} and [(dmpe)2MnH2(SiH2R)] {R = Ph (18Ph) or nBu (18Bu)} were generated by exposure of silylene hydride complexes, [(dmpe)2MnH(=SiR2)] (16R2), and disilyl hydride complexes, [(dmpe)2MnH(SiH2R)2] (20R), respectively, to H2 at room temperature. In solution, 18R and 18R2 exist as an equilibrium mixture of a central isomer with a meridional H–Si–H arrangement of the silyl and hydride ligands {this isomer may be considered to contain an η3-coordinated silicate (H2SiR3–) anion}, and a transHSi isomer with trans-disposed hydride and nonclassical hydrosilane ligands (the latter is the result of significant but incomplete hydrosilane oxidative addition). Additionally, DFT calculations indicate the thermodynamic accessibility of lateralH2 and transH2 isomers with cis- and trans-disposed silyl and dihydrogen ligands, respectively. Compounds 18Ph2 and 18Ph crystallized as the central isomer, whereas 18Bu crystallized as the transHSi isomer. Bonding in the central and transHSi isomers of 18R and 18R2 was further investigated through 29Si_edited 1H–1H COSY solution NMR experiments to determine both the sign and magnitude of J29Si,1H coupling (negative and positive values of J29Si,1H are indicative of dominant 1-bond and 2-bond coupling, respectively). These experiments afforded J29Si,1H coupling constants of –47 Hz for η3-(H2SiR3) in the central isomer of 18Et2 (calcd. –40 to –47 for 18R and 18R2), –38 to –54 Hz for η2-(R3Si–H) in the transHSi isomer of 18R and 18R2 (calcd. –26 to –47 Hz), and 5 to 9 Hz for the terminal manganese hydride ligand in the transHSi isomer of 18Et2, 18Ph, and 18Bu (calcd. 12 to 14 Hz for 18R and 18R2), experimentally supporting the nonclassical nature of bonding in the central and transHSi isomers. Exposure of disilyl hydride complexes 20R to diisopropylcarbodiimide {C(NiPr)2} afforded manganese(I) amidinylsilyl complexes [(dmpe)2Mn{κ2-SiHR(NiPrCHNiPr)}] {R = Ph (25Ph,H) or nBu (25Bu,H)}. DFT calculations and analysis of XRD bond metrics suggest that the structure of 25R,H involves a contribution from a resonance structure featuring a neutral base-stabilized silylene and an anionic amido donor on manganese. Reactions of 20R, as well as the silylene hydride complex 16Et2, with CO2 yielded the manganese(I) formate complex trans-[(dmpe)2Mn(CO)(κ1-O2CH)] (26), with a polysiloxane byproduct. Compound 26 was found to undergo reversible CO2 elimination at room temperature, and was only stable under an atmosphere of CO2. Complexes 25R,H and 26 were crystallographically characterized. Silyl, silylene, and silene complexes in this work were accessed via reactions of [(dmpe)2MnH(C2H4)] (10) with hydrosilanes, in some cases followed by ethylene. Therefore, ethylene (C2H4 and C2D4) hydrosilylation was investigated using [(dmpe)2MnH(C2H4)] (10) as a pre-catalyst, resulting in stepwise conversion of primary to secondary to tertiary hydrosilanes. Various catalytically active manganese-containing species were observed during catalysis, including silylene and silene complexes, and a catalytic cycle is proposed. The proposed catalytic cycle is unusual due to the involvement of silylene hydride and silene hydride complexes, potentially as on-cycle species. The reaction of [(dmpe)2MnH(C2H4)] (10) with H2 at 60 °C afforded ethane and the dihydrogen hydride complex [(dmpe)2MnH(H2)] (11), which has previously been prepared by an alternative route. Complex 10 reacted with hydroborane reagents 9-BBN or HBMes2 at 60 °C to afford EtBR2 and Mn(I) borohydride complexes [(dmpe)2Mn(μ-H)2BR2] (29: R2 = C8H14, 30: R = Mes); two intermediates were observed in each of these reactions. Deuterium labelling experiments using the deuterated hydroborane DBMes2 suggest that this reaction proceeds via the 5-coordinate ethyl isomer of 10; [(dmpe)2MnEt] (13). By contrast, exposure of 10 to BH3∙NMe3 required a higher temperature (90 °C) to yield [(dmpe)2Mn(μ-H)2BH2] (28), and ethylene was formed as the reaction byproduct; this reaction presumably proceeded by ethylene substitution. Deuterium incorporation into both the MnH and BH environments of 28 was observed under an atmosphere of D2 at 90 °C. Reactions of 10 with free dmpe yielded ethylene and a mixture of [{(dmpe)2MnH}2(μ-dmpe)] (31) and [(dmpe)2MnH(κ1-dmpe)] (32), which could be isolated by washing/recrystallization or sublimation, respectively. Similar reactivity was observed between 10 and HPPh2, which afforded ethylene and [(dmpe)2MnH(HPPh2)] (33) at 90 °C. Exposure of 10 to HSnPh3 yielded the manganese(II) stannyl hydride complex [(dmpe)2MnH(SnPh3)] (34) along with ethylene and, presumably, additional unidentified products. However, the mechanism for formation of 34 is unclear, it could not be isolated in pure form due to decomposition to form various species including SnPh4, and the mechanism of the decomposition process remains obscure. Previously reported complex 11, along with new complexes 28-31 and 33-34, were crystallographically characterized. This work provides valuable insights to unusual metal–ligand bonding motifs and reactions, and as such contributes to the fundamental understanding of organometallic chemistry. / Dissertation / Doctor of Philosophy (PhD) / The focus of this work is the synthesis and investigation of manganese-containing complexes with Mn–P, Mn–C, Mn–H, and/or Mn–Si linkages. Many of these complexes feature unusual bonding motifs, including the first group 7 complexes bearing an unstabilized silylene (:SiR2) ligand and the first 1st row transition metal complexes bearing an unstabilized silene (R2Si=CR2) ligand. Variable temperature Nuclear Magnetic Resonance (NMR) spectroscopy and X-ray crystallography were employed to investigate the structures of these complexes, while Density Functional Theory (DFT) calculations and trapping experiments were employed to understand the mechanisms for various unusual chemical transformations. Some of the complexes were evaluated for activity towards catalytic hydrosilylation of ethylene. This work provides valuable insights to unusual metal–ligand bonding motifs and reactions, and as such contributes to the fundamental understanding of organometallic chemistry.

Thesis advisor: Amir H. Hoveyda / Catalytic enantioselective reactions are of great importance in synthetic organic chemistry. Thus, development of efficient, selective and easily accessible catalyst for various bond formations is the main task in our laboratories. First, we have developed the first broadly applicable enantioselective boryl conjugate addition reactions to a variety of α,β-unsaturated carbonyls, promoted by a chiral Lewis basic N-heterocyclic carbene. The valuable β-boryl carbonyls were further used in complex molecule syntheses. The mechanism of these C–B bond formations was studied in details. We have also developed a practical method for enantioselective addition of an allene unit to aryl-, heteroaryl- and alkyl-substituted Boc-aldimines. These efficient C–C bond formations, catalyzed by an aminophenol-derived boron-based catalyst, were further utilized in succinct syntheses of anisomycin and epi-cytoxazone. Finally, chiral NHC–Cu complexes were employed for site-, diastereo- and enantioselective silyl conjugate additions to acyclic and cyclic dienones and dienoates. The precious enantiomerically enriched allylsilane obtained can be converted into a ketone-aldol type product, which is difficult to access through alternative methods. / Thesis (PhD) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Orientador: Luiz Carlos Dias / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-12T11:30:26Z (GMT). No. of bitstreams: 1 Ferreira_MarcoAntonioBarbosa_M.pdf: 7153235 bytes, checksum: e612e11ed109a87cf51fbc6e47852412 (MD5) Previous issue date: 2008 / Resumo: ADIÇÃO DE ENOLATOS DE BORO DE METILCETONAS A ALDEÍDOS. A presenca de um b-heteroatomo em enolatos de boro de metilcetonas tem forte influência na estereoquímica das reações aldólicas correspondentes. As reações aldólicas mediadas por enolatos de boro de metilcetonas com P = PMB com aldeídos aquirais conduziram a altos níveis de estereoindução remota 1,5-anti. No caso das metilcetonas com P = TBS e P = t-Bu, a adição dos enolatos de boro correspondentes a aldeídos quirais conduziu a uma mistura dos diastereoisômeros favorecendo os adutos de aldol 1,5-syn. A natureza do substituinte nos anéis aromáticos não teve influência significativa na estereoquímica das reações aldólicas, levando a resultados similares. LIGAÇÕES DE HIDROGÊNIO INTRA E INTERMOLECULARES DE ÉTERES ALQUÍLICOS E DE SILÍCIO: ESTUDO TEÓRICO E EXPERIMENTAL. Investigou-se o impacto eletrônico do grupo protetor P (TBS ou PMB) no equilíbrio conformacional dos álcoois (R)-metil substituídos 139 (P = TBS) e 140 (P = PMB). A análise conformacional e experimentos de H NMR para os álcoois 139 e 140 refletiram a tendência para a existência de confôrmeros apresentando ligação de hidrogênio. Mostrou-se que a magnitude da ligação de hidrogênio de éteres alquílicos e de silício são dependentes de diversas propriedades, como interação de orbitais, hibridização e energia dos pares de elétrons não ligantes do oxigênio, e não apenas pela ocupância eletrônica do átomo aceptor / Abstract: ADDITION OF BORON ENOLATES OF METHYLKETONES TO ALDEHYDES. The presence of a b-heteroatom substituent in the boron enolates of methylketones has a strong influence in the stereochemical outcome of the corresponding aldol reactions. The boron-mediated aldol reactions of methylketones with P = PMB were found to proceed with high degrees of remote 1,5-anti stereoinduction. In the case of methylketones with P = TBS and P = t-Bu, the corresponding boron enolates additions to aldehydes gives a mixture of aldol adducts favoring the 1,5-syn adducts. The nature of the substituent at the aromatic ring does not influence the stereochemical outcome, as p-OMe and p-NO2 lead to similar results.INTRA AND INTERMOLECULAR HYDROGEN BONDS IN ALKYL AND SILYL ETHERS: EXPERIMENTAL AND THEORETICAL ANALYSIS. We have investigated the electronic impact of the P protecting group (TBS or PMB) in the conformational equilibrium of (R)-methyl substituted alcohols 139 (P = TBS) and 140 (P = PMB). The conformational analysis and H NMR experiments for alcohols 139 and 140 reflect the tendency for the existence of hydrogen-bonded conformations. We showed that the extents of the hydrogen bonds in silyl and alkyl ethers are determined by several properties, such as orbital interactions, lone pair hybridizations, and lone pair energies, and not just by the electronic occupancy of the acceptor atom / Mestrado / Quimica Organica / Mestre em Química

A series of four novel halosilylsubstitued monocyclopentadienyl titanium complexes; [Si(CH3)2FCp]TiCl3 – FSiTTC, [Si(CH3)F2Cp]TiCl3 F2SiTTC, [Si(CH3)Cl2Cp]TiCl3 - Cl2SiTTC, [Si(CH3)2ClCp]TiCl3 - ClSiTTC was tested as catalytic precursors for polymerization of styrene in toluene. The maximum polymerization activity was achieved after polymerization period of 20 minutes. Activity decreased in order FSiTTC/MAO > F2SiTTC/MAO > Cl2SiTTC/MAO > ClSiTTC /MAO. Prepared polystyrenes were characterized using 13C NMR spectroscopy and DSC analysis. Syndiotacticity index of obtained PSs was determined by means of Soxhlet extraction with butan-2-one as solvent. Syndiotacticity indexes of PSs obtained by investigated catalysts possessed higher values then those obtained by standard catalysts (CpTiCl3 a Cp*TiCl3) at comparable polymerization conditions.

Deck and coworkers previously showed that Me3Si substituents adjacent to group 4 metallocene dichlorides (M = Ti, Zr, Hf) are converted to corresponding BrMe2Si groups using BBr3, and that these BrMe2Si substituents are highly reactive to nucleophilic reagents such as water. The high reactivity of the Si-Br bonds suggested that these substituents could react with hydroxyl groups on the surface of partially dehydroxylated silica, forming covalently immobilized metallocene catalysts. This dissertation concerns the synthesis of electrophile-functionalized zirconocene dihalide complexes and the use of functionalized zirconocene dihalides as precursors to silica-supported metallocene olefin polymerization catalysts. Our first objective was to extend the metallocene "functionalization" chemistry to obtain substituents bearing more than one electrophilic bond. The reactivities of Me3Sn and Ph2MeSi substituents were explored in detail. (Me3Sn)2C5H4 combined with CpZrCl3 in toluene to afford (h5-Me3Sn-C5H4)CpZrCl2 (A). Reactions of A with electrophiles (E-X = Cl2B-Cl, I-Cl, and I-I) afforded (ï ¨5-XMe2Sn-C5H4)CpZrCl2 (and E-Me) cleanly. The reaction of A with BBr3 afforded either (ï ¨5-BrMe2Sn-C5H4)CpZrBr2 (25 ï °C, 10 min) or (ï ¨5-Br2MeSn-C5H4)CpZrBr2 (25 ï °C, 15 h). Ph2MeSi-C5H4Li combined with ZrCl4·2THF to afford (h5-Ph2MeSi-C5H4)2ZrCl2 (B). The reaction of B with BCl3 led to incomplete cleavage of the Ph-Si bonds, however treatment of B with BBr3 afforded (h5-Br2MeSi-C5H4)2ZrBr2 (C) efficiently. The Sn-X bonds of the stannylated metallocenes were however relatively unreactive toward water and were excluded as candidates precursors for supported metallocene catalysts. X-ray crystal structures of (h5-ClMe2Sn-C5H4)CpZrCl2·½toluene, (h5-Br2MeSn-C5H4)CpZrBr2·THF, B, and C were obtained. The functionalized metallocene C reacts with water to afford an oligosiloxane-supported zirconocene dibromide. Combinations of solution 1H NMR, solid state CPMAS 13C NMR, and solid state CPMAS 29Si NMR spectroscopy suggested a stereoregular structure in which the metallocene units have local Cs (meso) symmetry. Although only sparingly soluble, the oligomeric substance showed activity for homogeneous ethylene polymerization (toluene solution, MAO cocatalyst, Al:Zr = 5000, 50 ï °C) similar to Cp2ZrCl2. Supported metallocene olefin polymerization catalysts were prepared by combining a functionalized metallocene precursor (Cp2ZrBr2 bearing either BrMe2Si or Br2MeSi groups) and partially dehydroxylated silica. Ethylene polymerization activity of the resulting catalysts was examined as a function of the precursor structure (number of reactive "tethering" groups, one vs. two Si-Br bonds per tethering group) and the immobilization conditions (time, temperature, presence or absence of NEt3 promoter). The activities of the immobilized zirconocene catalysts decreased and the stabilities increased with increasing number of tethers. The immobilized catalyst prepared from (ï ¨5-Br2MeSi-C5H4)2ZrBr2, which is assumed to form two "double-tethers" to silica, was significantly more active than the catalyst prepared from [ï ¨5-1,3-(BrMe2Si)2C5H3]2ZrBr2, which is assumed to form four "single-tethers" to silica. Catalyst leaching was observed in all the immobilized zirconocene catalysts. The use of NEt3 in the immobilization reaction enabled more metallocene to be supported, but the resulting activity was lower. The dissertation also includes model studies on the immobilization reaction and the stability of the Si-O-Si bonds. The reaction of C with tBuMe2SiOH results in the formation of Si-O-Si bonds; addition of NEt3 results in further reaction to afford Si-O-Zr bonds. The reaction of Reaction of Me3Si-O-SiMe3 with MAO showed that Si-O-Si bonds can be cleaved under the conditions of our polymerization reactions. / Ph. D.