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

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dc.contributor.advisorFoley, Stephen R.en_US
dc.creatorBoyd, Ramon Cornellen_US
dc.date.accessioned2007-01-23T11:43:15Zen_US
dc.date.accessioned2013-01-04T04:24:32Z
dc.date.available2007-01-23T08:00:00Zen_US
dc.date.available2013-01-04T04:24:32Z
dc.date.created2007-01en_US
dc.date.issued2007-01-22en_US
dc.date.submittedJanuary 2007en_US
dc.description.abstractTwo 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.en_US
dc.identifier.urihttp://hdl.handle.net/10388/etd-01232007-114315en_US
dc.language.isoen_USen_US
dc.subjectbulkyen_US
dc.subjectmigratory insertion mechanismen_US
dc.subjectcoordination/insertion methodologyen_US
dc.subjectd-block metalen_US
dc.subjectlate transition metalen_US
dc.subjectphenolic ringen_US
dc.subjectcoordination numberen_US
dc.subjectketimineen_US
dc.subjectprecatalystsen_US
dc.subjectketimine nitrogenen_US
dc.subjectbis(salicylaldiminato)copper(II)en_US
dc.subjectratioen_US
dc.subjectcyclopropaneen_US
dc.subjectsteric bulken_US
dc.subjectsalicylaldiminatoen_US
dc.subjectTMAen_US
dc.subjectsalten_US
dc.subjecttrimethylaluminumen_US
dc.subjectarylen_US
dc.subjectoilen_US
dc.subjectalkylen_US
dc.subjectcopper-arylsen_US
dc.subjectcopper-alkylsen_US
dc.subjectC-H activationen_US
dc.subjecthomolyticen_US
dc.subjecthomolytic cleavageen_US
dc.subjectcopper(II)en_US
dc.subjectpolymerizationen_US
dc.subjectethyleneen_US
dc.subjectcisen_US
dc.subjecttransen_US
dc.subjectsymmetryen_US
dc.subjectdiastereomeren_US
dc.subjectethyl trans-2-phenylcyclopropanecarboxylateen_US
dc.subjectsalicylaldimineen_US
dc.subjectSALen_US
dc.subjectEDAen_US
dc.subjectethyl diazoacetateen_US
dc.subjectstyreneen_US
dc.subjectcyclopropanationen_US
dc.subjectcopperen_US
dc.subjectdiastereoselectiveen_US
dc.subjectsteric protectionen_US
dc.subjectstableen_US
dc.subjectCH(SiMe3)2en_US
dc.subjectintermediateen_US
dc.subjectcatalytic activityen_US
dc.subjectassociated TMAen_US
dc.subjectfree TMAen_US
dc.subjectvacant coordination siteen_US
dc.subjecthydrolysisen_US
dc.subjectLewis aciden_US
dc.subjecthalogenen_US
dc.subjectanionicen_US
dc.subjectanionic liganden_US
dc.subjectdonor liganden_US
dc.subjectmonodentate anionic liganden_US
dc.subjectaluminum(III)en_US
dc.subjectmonodentateen_US
dc.subjectpolymer chainen_US
dc.subjectpolymeren_US
dc.subjectchainen_US
dc.subjectaluminum-carbon bonden_US
dc.subjectbulky SAL liganden_US
dc.subjectopen coordination siteen_US
dc.subjectfirst row transition metalen_US
dc.subjectPEen_US
dc.subjectparamagneticen_US
dc.subjecthigh molecular weight polyethyleneen_US
dc.subjectalkylateen_US
dc.subjectmethylaluminoxaneen_US
dc.subjectMAOen_US
dc.subjectanionic ligandsen_US
dc.subjectarylateen_US
dc.subjectaluminum carbonen_US
dc.subjectaluminum carbon bonden_US
dc.subjectbeta-hydrogen eliminationen_US
dc.subjectbeta hydrogen eliminationen_US
dc.subjectAufbau reactionen_US
dc.subjectAufbauen_US
dc.subjectneutral dialkyl aluminumen_US
dc.subjectaluminum-alkylen_US
dc.subjectaluminum alkylen_US
dc.subjectcopper(0)en_US
dc.titleInvestigations into cyclopropanation and ethylene polymerization via salicylaldiminato copper (II) complexesen_US
dc.type.genreThesisen_US
dc.type.materialtexten_US
thesis.degree.departmentChemistryen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Saskatchewanen_US
thesis.degree.levelMastersen_US
thesis.degree.nameMaster of Science (M.Sc.)en_US

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