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dc.contributor.advisorNolan, Steven P.
dc.contributor.authorUrbina-Blanco, César A.
dc.coverage.spatialxvii, 183en_US
dc.description.abstractAs part of a European wide effort to develop metathesis catalysts for use in fine chemical and pharmaceutical compound synthesis, this study focuses on the design and synthesis of ruthenium based catalysts for olefin metathesis. The aim, of this work was simple: to develop new, more active, more stable, easy to synthesise and commercially viable Ruthenium based catalysts, as well trying to rationalize the effect of structural changes on reactivity. Two different approaches were explored in order to develop more active catalysts bearing N-heterocyclic carbene (NHC) ligands: changing the leaving group and the effect of the NHC moiety in indenylidene type complexes. Over 12 new catalysts were developed and their activity compared to that of commercially available catalysts. Overall, the new complexes exhibited superior reactivity compared to previously reported catalysts in several benchmark transformations. However, olefin metathesis is a very substrate specific reaction, and rather than finding one catalyst that is superior to all, a catalogue of catalysts suitable for specific transformations was developed. In addition, the effect of structural changes on substrate activity was investigated in the ring closing metathesis of 1,8-nonadienes. The reaction profiling showcased the presence of a gem-difluoro group as an accelerating group in this incarnation of the olefin metathesis reaction and leads to ring formation over polymerization. In order to rationalize the effect of structural changes on catalyst activity, kinetic studies dealing with the initiation mechanism of ruthenium-indenylidene complexes were examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the ruthenium-based olefin metathesis reaction. These results highlight the importance of systematic development of catalysts and that as scientists we should not take for granted.en_US
dc.publisherUniversity of St Andrews
dc.subject.lcshRuthenium catalysts--Synthesisen_US
dc.subject.lcshMetathesis (Chemistry)en_US
dc.titleDesign and synthesis of ruthenium indenylidene-based catalysts for olefin metathesisen_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US

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