Johnson, Tarn C. (2012) Iron and ruthenium catalysts for hydrogen transfer reactions. PhD thesis, University of Warwick.

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Abstract

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
Official Date:	May 2012
Dates:	Date Event May 2012 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Wills, Martin
Sponsors:	Engineering and Physical Sciences Research Council (EPSRC)
Extent:	viii, 236 leaves : ill., charts
Language:	eng
URI:	http://wrap.warwick.ac.uk/id/eprint/50062

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