Aluminum- and gallium-bridged ansa-zirconocene compounds (Pytsi)Al[1]ZCP (31a) and (Pytsi)Ga[1]ZCP (31b) containing a bulky trisyl-based ligand with a pyridyl donor group [Pytsi = -C(SiMe3)2SiMe2(2-C5H4N)] were synthesized in 31% and 40% yield, respectively, by the reaction of (Pytsi)ECp2 [E = Al (29a), Ga (29b)] with Zr(NMe2)4 followed by reaction with Me3SiCl. Compounds 29a and 29b were prepared by the reaction of (Pytsi)ECl2 [E = Al (28a), E = Ga (28b)] with two equivalents of NaCp. The molecular structures of 29a and 29b were elucidated in solution by 1H and 13C NMR spectroscopy. Species 31a was characterized by multinuclear NMR spectroscopy while 31b was characterized by CHN elemental analysis, 1H and 13C NMR spectroscopy and mass spectrometry. Both species are the only known examples of aluminum- and gallium-bridged ansa-zirconocenes. Compound 31b in combination with MAO was applied and shown to be highly active for ethylene polymerization at room temperature. The activity of 31b was compared to that obtained for Cp2ZrCl2 using a glass reactor system and was found to be comparable. The influence of precatalyst concentration and ethylene pressure on activity of 31b was studied.

Membrane separations provide a potentially attractive technology over conventional processes due to their advantages, such as low capital cost and energy consumption. The goal of this thesis is to design hybrid membranes that facilitate specific gas separations, especially olefin/paraffin separations. This thesis focuses on the designing dendrimer-based hybrid membranes on mesoporous alumina for reverse-selective separations, synthesizing Cu(I)-dendrimer hybrid membrane to facilitate olefin/paraffin separations, particularly ethylene/methane separation, and investigating the influence of solvent, stabilizing ligands on facilitated transport membrane. Reverse-selective gas separations have attracted considerable attention in removing the heavier/larger molecules from gas mixtures. In this study, dendrimer-based chemistry was proved to be an effective method by altering dendrimer structures and generations. G6-PIP, G4-AMP and G3-XDA are capable to fill the alumina mesopores and slight selectivity are observed. Facilitated transport membranes were made to increase the olefin/paraffin selectivity based on their chemical interaction with olefin molecules. Two approaches were explored, the first was to combine facilitator Cu(I) with dendrimer hybrid membrane to increase olefin permeance and olefin/paraffin selectivity simultaneously, and second was to facilitate transport membrane functionality by altering solvents and stabilizing ligands. Promising results were found by these two approaches, which were: 1) olefin/paraffin selectivity slightly increased by introducing facilitator Cu(I), 2) the interaction between Cu(I) and dendrimer functional groups are better known.

Research on nanofluids has been undertaken for several years because of the reported enhancements of thermal properties such as thermal conductivity and enhanced heat transfer performance in laminar flow. Nanofluid is the fluid where nanoparticles are dispersed in a base fluid. Thermal conductivity and viscosity are considered to be the most prominent factors in the efficient use of nanofluids. A change in thermal conductivity and viscosity also changes the convective heat transfer coefficient. Nanoparticles can be metallic or non-metallic and also can have different shapes. In this study, Poly-Alpha-Olefin (PAO) has been used as a base fluid with Alumina (Al2O3) nanoparticles. Poly-Alpha-Olefin is commonly used for engine lubrication in military applications and cooling in electronic and industrial devices. Several nanofluid samples were made by METSS Corp. in Ohio, USA using different dispersants, different base fluids and different morphology of alumina nanoparticles. The mass fraction of nanoparticles is from 2.5 to 20 percent. The thermal properties of each sample such as thermal conductivity and viscosity have been measured. Thermal conductivity of nanofluids and pure base fluids were both measured and the thermal conductivity enhancement has been calculated. Also, the heat transfer coefficient has been determined for laminar flow under constant heat flux conditions. Results indicate that all the tested nanofluids and base fluid samples show a Newtonian behavior. Among the nanofluid samples, NF-048, which contains non-spherical Alumina nanoparticles exhibits the greatest thermal conductivity enhancement when compared to pure PAO. Heat transfer tests were conducted with pure PAO and NF-048, and an enhancement in convective heat transfer coefficient was observed. The thermal conductivity of NF-048 increases with temperature, which is consistent with heat transfer results. Furthermore, the percentage enhancement in convective heat transfer coefficient was shown to increase non-linearly with the axial distance in the heat transfer section. NF-048 exhibits a lower Re (Reynolds number)*Ra (Rayleigh number) than pure PAO under laminar flow constant heat flux conditions indicating that nanoparticle morphology and composition are the two main factors responsible for convective heat transfer enhancement at low Reynolds number.

The sterically expanded octamethyloctahydrodibenzofluorene moiety, C29H38 (Oct), has been incorporated into ansa-metallocenes and constrained geometry catalysts (CGC's). Utilization of this sterically expanded version of fluorene has resulted in solidstate anomalies for both systems. The ansa-metallocenes Me2C(n5-C5H4) (n5-C29H36)MCl2, M = Zr, Hf and Me2C(n5-C5H4)(n5-C29H36)ZrBn2 demonstrate crystal motifs expected for ansametallocenes while Me2C(n5-C5H4)(n5-C29H36)MMe2, M=Zr, Hf exhibit diffuse diffraction, a phenomenon that is extremely unusual for organometallic complexes. This crystalline anomaly is the result of a disorder restricted to two dimensions caused by the rare pillared motif of the system. The best solution for this system consists of parallel and anti-parallel pillars present in a 60:40 ratio. The solid state anomaly observed for the Oct-CGC's occurs on a molecular level. The parent Oct-CGC, Me2Si(1-C29H36)(1-N-tBu)ZrCl2·OEt2, demonstrates an unprecedented n1 ligation to the fluorenyl-based ring. Systematic derivatization of this system via halide substitution, alkylation, and exchange of Zr for Hf has revealed that the n1 ligation persists for systems with small substituents on the metal center capable of retaining a coordinated ether. It is hypothesized that the unusual structure of this new Oct-CGC results in Me2Si(1-C29H36)(1-N-tBu)ZrCl2·OEt2/MAO (MAO = methylaluminoxane) being six times more active in the homopolymerization of 1-octene than ethylene. When compared to the prototypical Ti-CGC Me2Si(n5-C5Me4)(n1-N-tBu)TiCl2/MAO, the Oct-CGC is 85 times more reactive in the homopolymerization of 1-octene and 52 times more active in the copolymerization of 1-octene and 4-methyl-1-pentene. The high reactivity of the Oct-CGC towards alpha-olefins results in the observation of an unyielding comonomer effect in the copolymerization of these olefins with ethylene. In addition, the Oct-CGC is perhaps the most syndioselective catalyst known. With an enantiofacial selectivity of 99.7% and a remarkably high activity towards alpha-olefins, the Oct-CGC is capable of producing the highest melting syndiotactic polypropylene (Tm = 165oC, annealed = 174oC) reported thus far. The high activity and syndioselectivity of the Oct-CGC can be extended to the production of syndiotactic poly(4-methyl-1-pentene) with the highest melting point thus far reported (Tm = 215oC).

In this dissertation, I have investigated applying the laser ablation of microparticle aerosol (LAMA) process to the production of nanocomposite polymer membranes for olefin/paraffin separation. Experimental results for three major thrusts are presented: 1) an investigation into the scalability of the LAMA process, 2) a new laser ablation technique for nanoparticle production from aqueous feedstocks, and 3) characterization of olefin-selective polymer nanocomposite membranes produced using LAMA. The propensity for Ag nanoparticles to form agglomerates in LAMA is investigated. Nanoparticle samples were collected on TEM grids at several feedstock aerosol densities. As the density increased, the particle morphology shifted from single nanoparticles 5 nm in diameter to chained agglomerates of 20 nm diameter primary particles. The results are in agreement with a numerical model of Brownian agglomeration and diffusion. Factors influencing nanoparticle morphology, such as temperature, initial nanoparticle charge, and feedstock aerosol density are discussed. It is shown that agglomeration occurs on a much longer timescale than the other processes, and can be treated independently. A new nanoparticle synthesis technique is presented: laser ablation of aqueous aerosols. A Collison nebulizer is used to generate a mist of ~10 [mu]m diameter water droplets containing dissolved transition metal salts. Water from the droplets quickly evaporates, leaving solid particles which are ablated by an excimer laser. Ablation results in plasma breakdown and photothermal decomposition of the feedstock material. For AgNO₃ ablated in He gas, metallic Ag nanoparticles were produced. For Cu(NO₃)₂ ablated in He gas, crystalline Cu₂O nanoparticles were produced. For Ni(NO₃)₂ ablated in He gas, crystalline NiO nanoparticles were produced. A combination of AgNO₃ and Cu(NO₃)₂ ablated in a reducing atmosphere of 10%H₂/He yielded nonequilibrium Ag-Cu alloy nanoparticles. Membranes composed of poly(ethylene glycol diacrylate) (PEGDA) and Ag nanoparticles were produced by the LAMA process. Permeation and sorption measurements for the light olefins and paraffins were conducted for these membranes. The membranes showed very little improvement in olefin/paraffin selectivity compared with neat PEGDA membranes. Using the LAMA implementation described here, it was impossible to produce membranes with high Ag loading. Whether membranes containing more Ag would exhibit improved selectivity remains an open question. / text

A reactive distillation column for the alkylation of benzene with long chain linear olefin was studied. The study involved design, construction, experimentation, and simulation of the column. Establishing the design required study of reaction rates, thermodynamic relationships, and packing structures. A heuristic was developed for the design of such columns. This heuristic involved estimating an amount of catalyst loading and subsequently determining the operating parameters for a column. This method is particularly applicable to systems with high concentrations of inert feeds. A column was constructed following the design. Data was collected from the column and compared to simulations. The simulations were performed with Aspen Plus RADFRAC. In this manner, the data was used to validate the commercial steady state models for reactive distillation. In addition, dynamic simulations of the system were performed. These dynamic simulations provided insight into more design considerations. For example, steady state simulations indicated an optimal feed stage based on steady state conversion of the olefin. However, the dynamic simulations showed a potential disadvantage to the utilization of the optimal feed stage. With some disturbances, a column configured with the feed stage with the highest steady state conversion also deviated from the steady state faster and with greater amplitude than other configurations. These considerations were further explored in developing a control scheme for reactive distillation columns. Control of reactive distillation differs from traditional distillation in that one control variable is conversion. Traditional distillation generally focuses on production rates and product purity. To this end, control schemes were analyzed and dynamic simulations were performed. These simulations showed an advantage to a variable pairing in which duty is paired with conversion. The conversion was inferred from a stage temperature in the reactive zone. In addition, distillate rate may be paired with product composition. In conclusion, the reactive distillation column design for long chain olefin alkylation of benzene requires careful estimation of catalyst requirements and valid simulation tools. In addition, dynamic response should be considered in the design. Finally, a simple inferential control scheme may be adequate. / text

The Laser Ablation of Microparticle Aerosols (LAMA) process produces nanoparticles by ablating microparticles that are entrained in an aerosol. Two of the main advantages of this process are that the particles produced are charged (preventing agglomeration) and bare (without a capping layer). Two different techniques are possible to collect the nanoparticles. In this work, the charged state of the particles formed was utilized to collect them electrostatically. This approach has the additional advantage that particles can be selected according to their size. The focus here was a particular application for gas separation. The nanoparticles produced were directly collected in a polymeric liquid, which was then irradiated with ultraviolet light to form a rubbery film. These membranes were tested for olefin/paraffin gas separation, a challenge that finds many applications, notably in the petroleum industry. / text

Despite previous extensive study of the widely-employed ruthenium-catalysed olefin metathesis reaction, the finer mechanistic details have not been elucidated. An area that is noticeably lacking is spectroscopic exploration of the relevant complexes. In this work, organometallic ruthenium complexes of importance to olefin metathesis have been investigated using Ru K-edge X-ray absorption spectroscopy. The lowest energy feature in the Ru K-edge spectrum has been unambiguously assigned as due to Ru 4d←1s transitions. These electric-dipole-forbidden transitions are extremely sensitive to geometry. For centrosymmetric complexes, the pre-edge feature has very low intensity because it is limited by the weak electric quadrupole mechanism. By contrast, non-centrosymmetric complexes exhibit a substantial increase in pre-edge intensity because Ru 5p-4d mixing introduces electric-dipole-allowed character to the Ru 4d←1s transitions. The energy of the edge feature in the Ru K-edge spectrum corresponds to ionisation of 1s electrons and is a good indicator of the charge on the metal centre. Unexpectedly, we found that the first-generation (L = PCy₃) Grubbs precatalyst (1) has a higher 1s ionisation energy than the second-generation (L = H₂IMes) complex (2). This effect provides a compelling rationale for the unexplained differences in phosphine dissociation kinetics for complexes 1 and 2: the phosphine dissociation rate of 2 is slower than 1 because the metal centre is more electron-deficient in 2. Density functional theory calculations confirm the charge differences and offer some insight into the nature of bonding in these complexes, particularly with regard to the N-heterocyclic carbene and trialkylphosphine ligands. On the basis of these results, we propose that, for this system, the NHC ligand is a weaker σ-charge donor than the phosphine ligand, and that the NHC accepts significant π-electron density from the metal; both interactions function to reduce the electron density on the ruthenium centre. An ultimate goal is to investigate reactive species in the olefin metathesis mechanism; accordingly, we have made considerable progress toward collecting XAS data for a metallacyclobutane species, and we are pursuing methods to trap the four-coordinate intermediate in the metathesis cycle.

Olefin/Paraffin separation, traditionally carried out by cryogenic distillation, is difficult to achieve due to the similar size and volatility of the components. Recently, many studies have explored membrane separation methods that utilize a metal ion to facilitate preferential olefin transport across the membrane. However, much of this work focuses on smaller molecules, C2-C3, which are gaseous at room temperature, while little work has been done studying separation of larger molecules, C5 and greater, which are generally liquid at room temperature. The processes developed to separate small molecules are not necessarily directly applicable to separate larger molecules. A polymer electrolyte membrane consisting of an active layer of polyethylene oxide (PEO) and silver tetrafluoroborate (AgBF4) has shown high selectivity for separating gaseous olefin/paraffin mixtures. The current project investigates the feasibility of applying this membrane to the separation of pentene and pentane (liquid C5 olefin and paraffin). Process variables investigated are the: pure component permeability ratio, equilibrium sorption uptakes, pure component diffusivities, and stable membrane lifetime. Permeation tests on individual species (n-pentane and 1-pentene) were performed in two operating modes with membranes of varying silver concentrations: direct liquid contact to the membrane, and vapour contact to the membrane. The vapour contact mode showed improved membrane stability in comparison to the liquid contact mode. The olefin/paraffin permeability ratio increases with increasing silver content in the membrane, however, the membrane selectivity is much lower than that achieved with smaller olefin/paraffin pairs. Selective chemical interactions between pentene and the membrane were observed, as the pentene sorption uptake is higher than that of pentane. In addition, a residual fraction is observed – a fraction of the pentene does not desorb from the membrane at ambient conditions – indicating a permanent or semi-permanent interaction. Desorption of pentane is determined to follow a Fickian diffusion model, while desorption of pentene appears to be governed by pseudo-second order kinetics.

The olefin metathesis reaction has become one of the most powerful carbon-carbon bond forming reaction in synthetic chemistry. This work has expanded the utility of olefin metathesis in metal coordination spheres in three major directions (1) the synthesis and characterization of trans-spanning bis(pyridine)PtCl2 complexes, (2) the developme-adducts of polyacetylene (PA), and (3) the development of regioregular -adducts of poly(phenylene-vinylene) (PPV). Chapter I gives a brief overview of olefin metathesis and previous applications to organometallic substrates. Chapter II details the synthesis of pyridine ligands containing alkenyl substituents, 2-NC5H4(CH2O(CH2)nCH=CH2) (n = 1, 2), 3-NC5H4(CH2O(CH2)nCH=CH2) (n = 1-5, 8, 9), and 3,5-NC5H3(p-C6H4O(CH2)7CH=CH2)2. Metalation of the new ligands with PtCl2 affords the corresponding trans-bis(pyridine)dichloroplatinum complexes, trans-PtCl2(2-NC5H4(CH2O(CH2)nCH=CH2))2 (n = 1, 2), trans-PtCl2(3-NC5H4(CH2O(CH2)nCH=CH2))2 (n = 1-5, 8, 9), and trans-PtCl2(3,5-NC5H3(p-C6H4O(CH2)7CH=CH2))2. Ring-closing metathesefirst generation catalyst followed by hydrogenations with Pd/C afford the title complexes trans-PtCl2-(NC5H4(CH2O(CH2)2n+2OCH2)H4C5N)] (n = 1, 2), trans-PtCl2-(NC5H4(CH2O(CH2)2n+2OCH2)H4C5N)] (n = 4, 8, 9), and trans-PtCl2-(NC5H3(p-C6H4O(CH2)12O-p-C6H4)2H3C5N)]. Reactions with methylmagnesium bromide afford trans-PtCl(CH3)(3-NC5H4(CH2O(CH2)nCH=CH2))2 (n = 2, 8) and trans-PtCl(CH3-(NC5H4(CH2O(CH2)nOCH2)H4C5N)] (n = 10, 18), which feature dipolar rotators. Low temperature NMR spectra in the latter remained facile on the NMR time scale in CDFCl2 at -120 degrees Celsius. Chapter III focuses on the application of ROMP with organometallic monomers to form metal pi-adducts of polyacetylene. The new complex (n4-benzene)Cp*Ir has been synthesized, crystallographically characterized, and evaluated in the ROMP reaction. Monomers (n4-benzene)CpIr, [(n6-COT)CpRu][PF6], and (n4-COT)Fe(CO)3 were also evaluated in the ROMP reaction. ROMP of (?4-benzene)CpIr with Grubbs' first generation catalyst afforded the conductive regioregular polymer CpIr-PA. Chapter IV focuses on the synthesis of the divinyl benzene complexes [Cp*Ir(C6H4(CH=CH2)2)][BF4]2 and [Cp*Ru(C6H4(CH=CH2)2)][OTf] and their polymerization via ADMET to afford PPV systems. Treatment of divinyl benzene ed the conductive regioregular polymers [Cp*Ir-PPV][BF4]2n and [Cp*Ru-PPV][OTf]n. The photophysical properties of the new -metal adducts of PPV exhibit blue-shifts relative to typical PPVs and retain strong UV absorption.