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

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      Date
      2007-01-22
      Author
      Boyd, Ramon Cornell
      Type
      Thesis
      Degree Level
      Masters
      Metadata
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      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.
      Degree
      Master of Science (M.Sc.)
      Department
      Chemistry
      Program
      Chemistry
      Supervisor
      Foley, Stephen R.
      Copyright Date
      January 2007
      URI
      http://hdl.handle.net/10388/etd-01232007-114315
      Subject
      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)
      Collections
      • Graduate Theses and Dissertations

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