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Towards the development of selective hydrocarbon oxygenation catalysts
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dc.contributor.advisor | Richens, David. T | |
dc.contributor.author | Guisado Barrios, Gregorio | |
dc.coverage.spatial | 240 | en_US |
dc.date.accessioned | 2010-06-21T15:16:11Z | |
dc.date.available | 2010-06-21T15:16:11Z | |
dc.date.issued | 2010-03-09 | |
dc.identifier | uk.bl.ethos.552400 | |
dc.identifier.uri | https://hdl.handle.net/10023/925 | |
dc.description.abstract | The synthesis of pure tris(6-hydroxymethyl-2-pyridylmethyl)amine (H₃L₁₁) is reported for the first time. New complexes of H₃L₁₁ with copper(II), manganese(II) and iron(III) have been characterised by X-ray crystallography. Linear [Fe₃(L₁₁)₂](ClO₄)₃ reveals the tightest Fe-O-Fe angle (87.6°) and shortest Fe...Fe distance (2.834 Å) presently found for a weakly antiferromagnetically-coupled high spin alkoxide-bridged polyiron(III) system. H₃L₁₁ provides a route to various hydrophobic peralkylated TPA ligand derivatives for creating a hydrophobic pocket for the assembly of iron catalysts for the novel 1-hydroxylation of n-alkanes. New 6-py substituted TPA ligands containing methyl (L₁₅) and n-octyl (L₁₆) ether linkages were synthesised via alkylation. Two further novel 6-py substituted ligands were synthesized incorporating n-hexyl substituents on one (L₂₁) and two (L₂₂) of the py moieties. Here a urea spacer group was used to promote hydrogen–bond assisted heterolytic O-O cleavage (generation of the potent FeV=O oxidant) within the hydroxoperoxoiron(III) precursor. High spin [FeII(L)(CH₃CN)[subscript(x)]](CF₃SO₃)₂ complexes (x = 0–2, L = L₁₅,₁₆,₂₁,₂₂) were characterised in solution by ¹H NMR. The structure of [Fe(L₂₂)](CF₃SO₃)₂ reveals a distorted iron(II) centre bound to four N atoms and two urea carbonyls. Iron(II) complexes of H₃L₁₁, L₁₅,₁₆,₂₁,₂₂ and tris(6-Br)-TPA (L₂₄), were investigated for catalysis of the oxygenation of cyclohexane by H₂O₂. Reaction of the iron(II) complexes with H₂O₂ and [superscript(t)]BuOOH was followed by time-resolved EPR and UV-VIS spectrophotometry. A correlation between the observed catalytic activity and the nature of the FeIII(L)-OOR intermediates generated is apparent. A convenient ‘one-pot’ synthesis of benzene-1,3,5-triamido-tris(l-histidine methyl ester) is reported along with attempts at preparing N,N’-bis(pyridylmethyl)-1,3- diaminopropane-2-carboxylic acid (L₂₅), a new water soluble pyridine-amine ligand. The final demetallation step resulted in ligand hydrolysis to the novel amino acid; 1,3-diaminopropane- 2-carboxylic acid which was characterised as its HCl salt by X-ray crystallography. | en_US |
dc.language.iso | en | en_US |
dc.publisher | University of St Andrews | |
dc.rights | Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported | |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/3.0/ | |
dc.subject | Oxidation | en_US |
dc.subject | Alkanes | en_US |
dc.subject | TPA derivatives | en_US |
dc.subject | Iron | en_US |
dc.subject | H₂O₂ | en_US |
dc.subject | [superscript(t)]BuOOH | en_US |
dc.subject | Hydrophobic pocket | en_US |
dc.subject.lcc | QD505.G8 | |
dc.subject.lcsh | Catalysts--Synthesis | en_US |
dc.subject.lcsh | Alkanes--Oxidation | en_US |
dc.subject.lcsh | Metalloenzymes | en_US |
dc.subject.lcsh | Cytochrome P-450 | en_US |
dc.subject.lcsh | Bleomycin | en_US |
dc.title | Towards the development of selective hydrocarbon oxygenation catalysts | en_US |
dc.type | Thesis | en_US |
dc.contributor.sponsor | Engineering and Physical Sciences Research Council (EPSRC) | en_US |
dc.type.qualificationlevel | Doctoral | en_US |
dc.type.qualificationname | PhD Doctor of Philosophy | en_US |
dc.publisher.institution | The University of St Andrews | en_US |
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