Investigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexes
Boyd, Ramon Cornell
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.
DegreeMaster of Science (M.Sc.)
SupervisorFoley, Stephen R.
Copyright DateJanuary 2007
migratory insertion mechanism
late transition metal
vacant coordination site
monodentate anionic ligand
bulky SAL ligand
open coordination site
first row transition metal
high molecular weight polyethylene
aluminum carbon bond
beta hydrogen elimination
neutral dialkyl aluminum
Showing items related by title, author, creator and subject.
INVESTIGATIONS INTO RARE 3-COORDINATE PALLADIUM COMPLEXES AND NEW APPLICATIONS OF COPPER IN COUPLING REACTIONS Chau, Tony (2014-06-20)In this thesis, the paper is divided into 2 parts, each corresponding to 2 individual projects. We started with looking into the synthesis of 3-coordinate palladium complexes incorporating a nacnac ligated system for ...
Olson, Jeremy Alan (2009)Aluminum complexes, specifically those employing bulky ligand frameworks such as sal (sal = 2-[CH═N(2,6-iPr2-C6H3)]-4,6-tBu2-phenoxide) and alpha-diimine (alpha-diimine = [(2,6-iPr2-C6H3)N═C(Me)]2) derivatives ...
Synthesis of £^-Diimine and iminoisoindoline ligands for applications in palladium and aluminum coordination chemistry and catalysis Chitanda, Jackson Mulenga (2009-11)This work began with the synthesis and full characterization of a novel £^-diimine ligand, (2,6-iPr2C6H3N=CH)2C6H4, from the reaction of o-phthaladehyde and the bulky aniline, 2,6-diisopropylaniline. It was observed that ...