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

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Date
2007-01-22Author
Boyd, Ramon Cornell
Type
ThesisDegree Level
MastersMetadata
Show full item recordAbstract
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
ChemistryProgram
ChemistrySupervisor
Foley, Stephen R.Copyright Date
January 2007Subject
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)
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