Iron and ruthenium catalysts for hydrogen transfer reactions
Johnson, Tarn C. (2012) Iron and ruthenium catalysts for hydrogen transfer reactions. PhD thesis, University of Warwick.
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The ruthenium catalysed oxidation of 1-phenylethanol derivatives with the release of hydrogen gas has been studied. A hydrogen acceptor was introduced in an effort to elucidate the rate-determining step of the reaction. The transfer of hydrogen from complex alcohols to simple aldehydes and ketones was pursued as a process for obtaining simple alcohols for fuel cell applications. The Shvo catalyst was identified as being the most efficient catalyst for the oxidation of difficult substrates. A family of iron analogues of the Shvo catalyst were synthesised and studied as precatalysts for the oxidation of alcohols. Catalyst activation was achieved by the removal of a CO ligand using trimethylamine-N-oxide and the oxidation of 1-phenylethanol derivatives with acetone was studied. Simple aldehydes were evaluated as hydrogen acceptors and a novel formylation reaction was discovered. Asymmetric iron analogues of the Shvo catalyst were synthesised and applied to the asymmetric transfer hydrogenation of acetophenone using 5:2 formic acid/triethylamine. The synthesis of further analogues with a tethering group was investigated to improve catalyst stability and enantioselectivity. Novel chiral diamine and amino-alcohol ligands containing 1,2,3-triazole functionalities were developed as ligands for the asymmetric transfer hydrogenation of ketones. Tridentate diaminotriazoles provided the best activity and selectivity in the reduction reactions with Ru3(CO)12.
|Item Type:||Thesis or Dissertation (PhD)|
|Subjects:||Q Science > QD Chemistry|
|Library of Congress Subject Headings (LCSH):||Iron catalysts, Ruthenium, Catalysts, Oxidation|
|Institution:||University of Warwick|
|Theses Department:||Department of Chemistry|
|Sponsors:||Engineering and Physical Sciences Research Council (EPSRC)|
|Extent:||viii, 236 leaves : ill., charts|
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