Show simple item record

dc.contributor.advisorMcDonald, Aidan
dc.contributor.authorSpedalotto, Giuseppe
dc.date.accessioned2021-03-30T10:48:10Z
dc.date.available2021-03-30T10:48:10Z
dc.date.issued2021en
dc.date.submitted2021
dc.identifier.citationSpedalotto, Giuseppe, High-valent dinuclear bis-μ-hydroxo complexes for PCET reactivity, Trinity College Dublin.School of Chemistry, 2021en
dc.identifier.otherYen
dc.identifier.urihttp://hdl.handle.net/2262/95935
dc.descriptionAPPROVEDen
dc.description.abstractHigh valent dinuclear bis-μ-hydroxo transition metals complexes are hypothesised to play a potentially crucial role in several enzymatic mechanism involving their high-valent dinuclear bis-μ-oxo counterparts such as soluble Methane Monooxygenase (sMMO) and Tyrosinase. However, even though late transition metals such as Ni and Cu, are postulated to be extremely powerful oxidants, an overall dearth of high-valent late transition metals μ-hydroxo model systems is present in literature. Herein we report the synthesis and characterization of the first example of high valent bis(μ-hydroxo)NiIII2 and the mixed valent bis(μ-hydroxo)MIIMIII complexes (M = Ni, Cu). The complexes were prepared from low-valent precursors supported by a novel dicarboxamidate ligand and were characterised using X-ray absorption and electron paramagnetic resonance spectroscopies, mass spectrometry, and DFT calculations. These techniques confirmed the oxidation states of the metal sites in the complexes and showed the retention of the bis(μ-hydroxide) diamond core in the high valent species. Reactivity studies were performed, demonstrating that both high valent bis(μ-hydroxo)NiIII2 and the mixed valent bis(μ-hydroxo)MIIMIII (M = Ni, Cu) complexes were powerful oxidants towards oxidative activation of phenolic O-H bonds. Thorough kinetic analysis of these reactions showed that the high-valent complexes were able to react through a hydrogen atom transfer mechanism.en
dc.language.isoenen
dc.publisherTrinity College Dublin. School of Chemistry. Discipline of Chemistryen
dc.rightsYen
dc.subjecthigh-valent dicopperen
dc.subjecthigh-valent dinickelen
dc.subjectbis-u-hydroxoen
dc.subjectPCETen
dc.subjectreactivityen
dc.subjectmixed-valent dinickelen
dc.titleHigh-valent dinuclear bis-μ-hydroxo complexes for PCET reactivityen
dc.typeThesisen
dc.type.supercollectionthesis_dissertationsen
dc.type.supercollectionrefereed_publicationsen
dc.type.qualificationlevelDoctoralen
dc.identifier.peoplefinderurlhttps://tcdlocalportal.tcd.ie/pls/EnterApex/f?p=800:71:0::::P71_USERNAME:SPEDALOGen
dc.identifier.rssinternalid226532en
dc.rights.ecaccessrightsopenAccess
dc.contributor.sponsorEuropean Research Council (ERC)en


Files in this item

Thumbnail
Thumbnail

This item appears in the following Collection(s)

Show simple item record