Global ETD Search

191	Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes Boyd, Ramon Cornell 23 January 2007 (has links) Two distinct overall research objectives are in this Masters thesis. Very little relates the two chapters apart from the ligands. The first chapter addresses diastereoselective homogeneous copper catalyzed cyclopropanation reactions. Cyclopropanation of styrene and ethyl diazoacetate (EDA) is a standard test reaction for homogeneous catalysts. Sterically bulky salicylaldimine (SAL) ligands should select for the ethyl trans-2-phenylcyclopropanecarboxylate diastereomer. Steric bulk poorly influences trans:cis ratios. Salicylaldiminine ligands do not posses the correct symmetry to affect diastereoselectivity. The SAL ligand belongs to the Cs point group in the solid state. Other ligand motifs are more effective at altering the trans:cis ratios. The second chapter addresses the general route toward successful copper(II) ethylene polymerization catalysts. Catalytic activity of the copper(II) complexes is very low. Polymer chain growth from a copper catalyst is very unlikely. Copper-carbon bonds decompose by homolytic cleavage or C-H activation. Copper-alkyls and aryls readily decompose into brown colored oils and salts with different colors. Ligand transfer to trimethylaluminum (TMA) appears to explain low yield ethylene polymerization. bulky migratory insertion mechanism coordination/insertion methodology d-block metal late transition metal phenolic ring coordination number ketimine precatalysts ketimine nitrogen bis(salicylaldiminato)copper(II) ratio cyclopropane steric bulk salicylaldiminato TMA salt trimethylaluminum aryl oil alkyl copper-aryls copper-alkyls C-H activation homolytic homolytic cleavage copper(II) polymerization ethylene cis trans symmetry diastereomer salicylaldimine SAL EDA ethyl diazoacetate styrene cyclopropanation copper diastereoselective steric protection stable CH(SiMe3)2 intermediate catalytic activity associated TMA free TMA vacant coordination site hydrolysis Lewis acid halogen anionic anionic ligand donor ligand monodentate anionic ligand aluminum(III) monodentate polymer chain polymer chain aluminum-carbon bond bulky SAL ligand open coordination site first row transition metal PE paramagnetic high molecular weight polyethylene alkylate methylaluminoxane MAO anionic ligands arylate aluminum carbon aluminum carbon bond beta-hydrogen elimination beta hydrogen elimination Aufbau reaction Aufbau neutral dialkyl aluminum aluminum-alkyl aluminum alkyl copper(0)
192	Model metropolitní optické sítě / Model of the metropolitan optical network Prudík, Jiří January 2008 (has links) The purpose of this master’s thesis is foremost to provide a simple guide how to build elements of optical metropolitan area network. The basic model consists to sequence of construction, network topology, passive and active parts. The collection contains examples of alternative technology such as Wireless LAN with different frequency. The optical network construction based on optical cable, fibres, splices, trays, adapters, connectors and active parts for example a lot of media convertor models. After that there are demonstrating type of wavelength division multiplexer used in metropolitan area network – passive planar PCL splitter. One of the passive planar splitter are used to increase optical fibre channel. At the end of the collection a simplified examples of used measurements – optical time domain reflectometry and optical fibre transmission. Contains standard protocols or reflectogram. The conclusion of this thesis summarizes costs of FTTb (Fibre To The Building) model of optical metropolitan area network in Czech republic and future contribution for society.

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Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes

Model metropolitní optické sítě / Model of the metropolitan optical network