The reactions of palladium are invaluable to modern academic and industrial research, and nanotechnology is the foundation on which the next generation of materials is built upon. Unsupported thiolate-capped palladium nanoparticles were found to be highly substrate selective for alkene hydrogenation and isomerization. A modified Brust-Schiffrin reaction enabled the facile and convenient synthesis of a diverse set of ultra-small thiolate-capped nanoparticles. The physical properties of these nanoparticles were highly tunable due to the widespread availability of ligand precursors. Mechanistic evidence and insights reveal that steric and electronic effects from the ligand environment on the nanoparticle surface controlled reactivity by influencing alkene adsorption via π bond coordination or di-σ bond formation. Only alkenes close enough to the metal surface of the nanoparticles underwent reaction. Dienes with good overlapping p orbitals could overcome these steric effects on the deactivated palladium nanoparticle surfaces. A mechanistic model was built from these completed studies, and this model can be used to predict the selectivity of hydrogenation or isomerization in multiple classes of alkenes with varied substitution patterns. These palladium nanoparticles were also found to be capable of chemoselective alkene hydrogenation in the presence of functional groups that are known to be labile towards reduction by palladium.
|Commitee:||Li, Lijuan, Buonora, Paul T|
|School:||California State University, Long Beach|
|Department:||Chemistry and Biochemistry|
|School Location:||United States -- California|
|Source:||MAI 81/1(E), Masters Abstracts International|
|Subjects:||Nanotechnology, Organic chemistry|
|Keywords:||alkenes and dienes, catalysis, hydrogenation, isomerization, nanomaterial, palladium|
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