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dc.contributor.advisorCole-Hamilton, D. J. (David John)
dc.contributor.advisorEastham, Graham
dc.contributor.authorParnham, Benjamin L.
dc.coverage.spatialxvii, 231 p.en
dc.date.accessioned2007-05-03T16:01:21Z
dc.date.available2007-05-03T16:01:21Z
dc.date.issued2007-06-20
dc.identifieruk.bl.ethos.551991
dc.identifier.urihttp://hdl.handle.net/10023/325
dc.description.abstractPalladium complexes of bis(di-tert-butylphosphinomethyl)benzene (DTBPMB) show remarkably high activity as alkene methoxycarbonylation catalysts, in addition to numerous other catalytic conversions, and are currently being commercialised by Lucite in ethene methoxycarbonylation to methyl propanoate. Any large-scale exploitation of this catalyst system for heavier products, however, is likely to be hindered by catalyst-product separation problems common to homogeneous catalysts; hence modification of this catalyst system to allow facile product separation was investigated. Tethering of DTBPMB residues onto polystyrene via Suzuki-type coupling of suitable precursors onto bromopolystyrene and boronic acid functionalised polystyrene resins was investigated and the phosphine was successfully immobilised. Phosphination of the resins was not complete however and as such there is concern that other phosphine residues may be present which do not exhibit a bidentate binding motif. The synthesis of a potassium sulfonate derivative of DTBPMB (KBPMBS) was successful and immobilisation of this onto ion exchange resins was also investigated. Some preliminary results from studies into 1-octene methoxycarbonylation using palladium complexes of these resins were obtained. Supporting of this diphosphine onto silica via a sol-gel co-condensation methodology was also investigated; the synthesis of a suitably functionalised precursor containing a sulfonamide linkage was successful via protection of the diphosphine using borane. Although formation of the silica support was successful, attempts to deprotect the phosphine-borane resulted in cleavage of the ligand from the support. An alternative route to this supported ligand was attempted and others discussed. Synthesis of a suitable sol-gel precursor via alkene hydrosilation was also attempted and is discussed. Supporting of the sulfonated phosphine, KBPMBS onto silica functionalised with imidazolium tethered residues was also investigated, although complete leaching of the phosphine from the support by methanol washing was observed. Immobilisation of the synthesised KBPMBS ligand in an ionic liquid (IL) phase was investigated. Complex formation and catalytic activity were demonstrated and a positive effect on conversion was observed upon addition of carbon dioxide to the system; possibly due to the increased CO solubility within the IL phase. Efficient product separation from the IL-immobilised catalyst system was demonstrated, both by organic extraction and using supercritical carbon dioxide flow. However, poor catalyst stability under these conditions appears to present a barrier to recycling this system, with loss of conversion observed on catalyst recycling. Other attempts to immobilise the DTBPMB ligand are discussed and reduction of the sulfide derivative of DTBPMB was demonstrated using hexachlorodisilane, which could be used as a general synthetic strategy for protecting highly electron rich phosphines. It is possible that increasing the bulk of the DTBPMB ligand may increase catalyst stability and result in catalyst systems with higher turnover numbers. Therefore syntheses of bulky ligands based on the DTBPMB backbone were investigated. 1,2,4,5-tetrakis(di(tert-butyl)phosphinomethyl)benzene was successfully synthesised although palladium complexes of this showed no activity in catalytic methoxycarbonylation. Attempts to synthesise a related biphenyl-based tetraphosphine is also discussed, although isolation of this in a pure form was not achieved. Routes toward tetraphenyl and dimethyl-diphenyl functionalised derivatives of DTBPMB have also been explored, although only a monophosphine was isolated due to difficulties in obtaining an intermediate di(chloromethyl) precursor in both synthetic pathways, although this now appears to have been overcome.en
dc.format.extent2675 bytes
dc.format.mimetypeapplication/pdf
dc.language.isoenen
dc.publisherUniversity of St Andrews
dc.subjectImmobilisationen
dc.subjectLuciteen
dc.subjectBis(di-tert-butylphosphinomethyl)benzeneen
dc.subjectSol gelen
dc.subjectIonic liquidsen
dc.subjectSupercriticalen
dc.subjectPhosphine synthesisen
dc.subjectMMAen
dc.subject.lccQD505.P2
dc.subject.lcshCatalystsen
dc.subject.lcshPhosphorous compoundsen
dc.subject.lcshMethyl methacrylateen
dc.titleModification of bis(ditertiarybutylphosphinomethyl)benzene for improved catalyst separation and stabilityen
dc.typeThesisen
dc.contributor.sponsorLucite Internationalen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD Doctor of Philosophyen
dc.publisher.institutionThe University of St Andrewsen
dc.publisher.departmentLucite Internationalen


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