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dc.contributor.advisorClarke, Matt
dc.contributor.authorLamb, Gareth W.
dc.coverage.spatial159en
dc.date.accessioned2008-12-02T16:51:14Z
dc.date.available2008-12-02T16:51:14Z
dc.date.issued2008-06-25
dc.identifieruk.bl.ethos.552150 
dc.identifier.urihttps://hdl.handle.net/10023/574
dc.description.abstractThe carbonylation of methanol to acetic acid is one of the most important applications in homogeneous catalysis. The first chapter comprises a review on the mechanistic studies into the catalytic cycle of the ‘Monsanto process’ and includes some of the most prominent studies into the use of phosphines in the rhodium-catalysed carbonylation of methanol. The second chapter of this thesis reports on an investigation into the application of rhodium complexes containing several C4 bridged diphosphines, namely BINAP, dppb, dppx and dcpb as catalysts for hydrogen tolerant methanol carbonylation. An investigation into the structure, reactivity and stability of pre-catalysts and catalyst resting states of these complexes has also been carried out. The origin of this hydrogen tolerance is explained based on the differing reactivities of the Rh acetyls with hydrogen gas, and by considering the structure of the complexes. In the third chapter I report on an investigation into how electronic properties and coordination mode affect the elimination of phosphonium salts from rhodium complexes. The stability of a range of monodentate, bidentate and tridentate rhodium-phosphine complexes was tested. I also report on the formation of a novel bidentate complex containing a partially quaternised TRIPHOS ligand and investigate the mechanism of formation using 13CH3I. Strong evidence is also presented supporting a dissociative mechanism as the means of phosphine loss from the rhodium centre. In the final chapters I report an investigation into the stability of rhodium-aminophosphine ligand complexes and into increasing the solubility of potential rhodium pre-catalysts through the use of amine-containing phosphine ligands.en
dc.format.extent3193 bytes
dc.format.mimetypeapplication/pdf
dc.language.isoenen
dc.publisherUniversity of St Andrews
dc.rightsCreative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/
dc.subjectRhodiumen
dc.subjectCatalysisen
dc.subjectHomogeneousen
dc.subjectAcetic aciden
dc.subjectCarbonylationen
dc.subjectMethanolen
dc.subjectEthanoic aciden
dc.subjectPhosphineen
dc.subjectLiganden
dc.subjectPhosphorousen
dc.subjectMonsantoen
dc.subjectCatalysten
dc.subject.lccQD505.L2en
dc.subject.lcshAcetic acid--Synthesisen
dc.subject.lcshRhodium catalystsen
dc.subject.lcshCatalysisen
dc.subject.lcshMethanolen
dc.subject.lcshPhosphineen
dc.titlePhosphine modified rhodium catalysts for the carbonylation of methanolen
dc.typeThesisen
dc.contributor.sponsorEngineering and Physical Sciences Research Council (EPSRC)en
dc.contributor.sponsorBritish Petroleum Companyen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD Doctor of Philosophyen
dc.publisher.institutionThe University of St Andrewsen


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Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported
Except where otherwise noted within the work, this item's licence for re-use is described as Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported