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Tantalum Carbene and Imide Complexes. Synthesis, Characterization, and Pathways of FormationAbbott, Julia Kathryn Covington 01 December 2010 (has links)
This dissertation focuses on two different types of organometallic compounds, carbenes and imides. The first project deals with the archetypal Schrock carbene, and the second project studies complexes that contain metal-nitrogen bonds, both amides and imides.
A summary of the research in this dissertation is discussed in Chapter 1. Chapter 2 begins the studies of the archetypal Schrock carbene (ButCH2)3Ta=CHBut. The studies include the synthesis of deuterated compounds (ButCD2)3TaCl2 and ButCD2Li, observation and identification of the intermediate, Ta(CD2But)5, and kinetic studies of the conversion of Ta(CD2But)5 to (ButCD2)3Ta=CDBut, giving the activation parameters and a kinetic isotope effect for the conversion. The work here confirms that the pentaneopentyltantalum is the precursor to the archetypal Schrock carbene.
Chapter 3 studies the effects of isotopic substitution on NMR chemical shifts of complexes in Chapter 2. Conformations of (ButCD2)3TaCl2 and Ta(CD2But)5 have also been investigated.
Chapter 4 begins the study of compounds containing metal-nitrogen bonds. Guanidinate imides Ta(NMe2)(=NSiMe3)[RNC(NMe2)NR]2 (R = Cy, Pri) have been prepared from the reactions of Ta(NMe2)4[N(SiMe3)2] with two equivalents of carbodiimides, RN=C=NR. The two guanidinate imides have been characterized by NMR spectroscopy and elemental analysis. In addition, the structure of Ta(NMe2)(=NSiMe3)[CyNC(NMe2)NCy]2 has been studied by single crystal X-ray diffraction. Under heating, Ta(NMe2)4[N(SiMe3)2] undergoes an unprecedented elimination of Me3Si-NMe2, converting the amide ligand –N(SiMe3)2 to the imide ligand =NSiMe3 to give an intermediate Ta(NMe2)3(=NSiMe3). In the presence of CyN=C=NCy, the carbodiimide captures the intermediate to give another intermediate Ta(NMe2)2(=NSiMe3)[CyNC(NMe2)NCy]. Subsequent second carbodiimide insertion leads to the formation of the final product Ta(NMe2)(=NSiMe3)[CyNC(NMe2)NCy]2. The remaining amide ligand, –NMe2, in Ta(NMe2)(=NSiMe3)[CyNC(NMe2)NCy]2 and Ta(NMe2)(=NSiMe3)[PriNC(NMe2)NPri]2 gives two separate resonances in the proton NMR spectrum at room temperature indicating inequivalence of the two methyl groups. The interconversion of the methyl groups in the former has been studied with variable-temperature NMR.
Chapter 5 studies the synthesis and characterization of metal cage complexes [(Me2N)3MO]4 (M = Nb, Ta). Single crystal X-ray diffraction studies show a cubane-like structure with M-O bridges. Variable-temperature NMR of the inequivalent amide methyl groups –NMeAMeB has also been carried out to find the activation parameters for the exchange.
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N-Heterocyclic Carbenes of the Late Transition Metals: A Computational and Structural Database StudyBaba, Eduard 05 1900 (has links)
A computational chemistry analysis combined with a crystallographic database study of the bonding in late transition metal N-heterocyclic carbene (NHC) complexes is reported. The results illustrate a metal-carbon bond for these complexes, approximately 4% shorter than that of a M-C single bond found in metal alkyl complexes. As a consequence of this result, two hypotheses are investigated. The first hypothesis explores the possibility of multiple-bond character in the metal-carbon linkage of the NHC complex, and the second, considers the change in the hybridization of the carbenoid carbon to incorporate more p character. The latter hypothesis is supported by the results. Analysis of these complexes using the natural bond orbital method evinces NHC ligands possessing trans influence.
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Polypropylene Modified by Polydimethylsiloxane in Catalytic Cross Metathesis ReactionsWu, Yan Rong January 2010 (has links)
In this study, we were particularly interested in looking at the possibility that cross metathesis of olefins in melt phase could be used to produce polydimethylsiloxane (PDMS) modified polypropylene (PP). The intention of this project was also to study and quantify relationships among the main experimental factors in the reaction: temperature, catalyst concentration and molar ratio of PP to PDMS, through a 2-level factorial statistical design.
In order to examine if PP-PDMS copolymers were synthesized in the melt phase, measurement of the chemical, physical and viscoelastic properties of the synthesized copolymers was necessary. Techniques including proton (¹H)-nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), rheometry and scanning electron microscopy (SEM), were all used to characterize the synthesized copolymers. ¹H NMR measurements confirmed the presence of PDMS in the copolymers. They also provided a quantitative measurement of PP to PDMS molar ratio in copolymers by determining the integration of PP PDMS repeating unit signals in NMR spectra. Compared to virgin PP, a lower melting enthalpy of the PP phase in the copolymer was observed from DSC results. This implied that the PDMS component influenced the thermal behavior of the PP crystalline phase in the copolymers. Moreover, TGA measurements indicated that a higher thermal stability was obtained for PP-PDMS copolymers than that for virgin PP wax and this was expected since PDMS is known for its excellent stability at high temperature. Rheological analysis showed that the presence of PDMS in the copolymers gave lower complex viscosities and loss moduli, but higher storage moduli than those for virgin PP. Furthermore, the morphology of copolymers was examined by SEM and elemental analysis at the surface using an energy dispersive X-ray (EDX) analyzer on the SEM. It was found that micrographs of copolymers showed round domains on the surface, which were not observed in virgin PP wax and those round segments were confirmed to contain silicon. Torque values used in a batch mixer for polymerizations and the remaining weight % of copolymers at 350°C were used to conduct statistical analysis, through which models used to describe the relationships between experimental factors and these physical responses were determined.
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Polypropylene Modified by Polydimethylsiloxane in Catalytic Cross Metathesis ReactionsWu, Yan Rong January 2010 (has links)
In this study, we were particularly interested in looking at the possibility that cross metathesis of olefins in melt phase could be used to produce polydimethylsiloxane (PDMS) modified polypropylene (PP). The intention of this project was also to study and quantify relationships among the main experimental factors in the reaction: temperature, catalyst concentration and molar ratio of PP to PDMS, through a 2-level factorial statistical design.
In order to examine if PP-PDMS copolymers were synthesized in the melt phase, measurement of the chemical, physical and viscoelastic properties of the synthesized copolymers was necessary. Techniques including proton (¹H)-nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), rheometry and scanning electron microscopy (SEM), were all used to characterize the synthesized copolymers. ¹H NMR measurements confirmed the presence of PDMS in the copolymers. They also provided a quantitative measurement of PP to PDMS molar ratio in copolymers by determining the integration of PP PDMS repeating unit signals in NMR spectra. Compared to virgin PP, a lower melting enthalpy of the PP phase in the copolymer was observed from DSC results. This implied that the PDMS component influenced the thermal behavior of the PP crystalline phase in the copolymers. Moreover, TGA measurements indicated that a higher thermal stability was obtained for PP-PDMS copolymers than that for virgin PP wax and this was expected since PDMS is known for its excellent stability at high temperature. Rheological analysis showed that the presence of PDMS in the copolymers gave lower complex viscosities and loss moduli, but higher storage moduli than those for virgin PP. Furthermore, the morphology of copolymers was examined by SEM and elemental analysis at the surface using an energy dispersive X-ray (EDX) analyzer on the SEM. It was found that micrographs of copolymers showed round domains on the surface, which were not observed in virgin PP wax and those round segments were confirmed to contain silicon. Torque values used in a batch mixer for polymerizations and the remaining weight % of copolymers at 350°C were used to conduct statistical analysis, through which models used to describe the relationships between experimental factors and these physical responses were determined.
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