Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes
type: CreativeWork
description: Two distinct overall research objectives are in this Master’s 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.
abstract: Two distinct overall research objectives are in this Master’s 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.
author: Boyd, Ramon Cornell
language: en_US
keywords: 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, ethyl trans-2-phenylcyclopropanecarboxylate, 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)
date published: 2007-01-22
date modified: 2026-07-24T04:26:52Z
provider: University of Saskatchewan
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Saskatchewan

PropertyValue
property ID: Handle
value: https://hdl.handle.net/10388/etd-01232007-114315