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The Synthesis and Characterisation of Manganese Amine Complexes

dc.contributor.authorBhula, Rajumati
dc.date.accessioned2008-08-20T03:38:40Z
dc.date.accessioned2022-11-01T23:54:17Z
dc.date.available2008-08-20T03:38:40Z
dc.date.available2022-11-01T23:54:17Z
dc.date.copyright1989
dc.date.issued1989
dc.description.abstractThe synthesis of a series of new manganese amine complexes is described. The reactions involve both macrocyclic and linear amines, together with acetato and benzoato ligands, Complexes ranging in nuclearity from one to possibly eighteen, and oxidation states II to IV, including mixed valent states, resulted. The characterisation of the products using infrared, ultraviolet-visible, and e.s.r spectral methods, as well as X -ray structural analysis and preliminary electrochemical studies are reported. In many cases, difficulty was encountered in obtaining crystals which were suitable for single crystal X- -ray studies, and the structural analysis of only four complexes is discussed. Further X -ray investigations are continuing. Complex 6, [Mn3(dien)3(CH3COO)2O3]I3 CH3OH.H2O is an oxo-centred Mn(III) trimer with an interesting feature, a µ2-peroxide bridge between two of the manganese atoms. The implications. of this structure upon. the current state of the inorganic model approach to the water oxidising centre of PS II is discussed. The structural description of a novel heptanuclear mixed-valence Mn(II, III) complex, 16, [Mn7(trien)2(dien)2(CH3COO)8O4](PF6)4.2H2O is reported. The core of this complex incorporates two Mn4(µ2-O)2 units, one inverted with respect to the other, and sharing a common manganese atom. Hence the core has been coined a 'siamese-twin butterfly'. In the reaction resulting in this oxidative deamination reaction were identified using n.m.r., gas chromatography and mass spectrometry. The structure of a valence-trapped hexameric complex, 25, [Mn6(3,2,3-tet)4(CH3COO)3)6]I5 4THF 2H2O is also discussed. The core of this complex is composed of a central Mn(III4)(µ3-O)2 unit with two peripheral di-µ2-oxo bridged Mn(IV) atoms. The formulation of this complex is also shared with several of the other 2,3,2 -tet and 3,2,3 -tet complexes investigated. The only monomeric complex to be synthesised, 28, Mn(3,2,3-tet)(IOBz)2]ClO4, was also. structurally investigated. Here, 3-iodobenzoate was used and in the resulting complex, the benzoate ligands are coordinated in a unidentate fashion, which was not observed in the other complexes. The amine occupies four planar sites around the central Mn(III) atom.en_NZ
dc.formatpdfen_NZ
dc.identifier.urihttps://ir.wgtn.ac.nz/handle/123456789/28226
dc.languageen_NZ
dc.language.isoen_NZ
dc.publisherTe Herenga Waka—Victoria University of Wellingtonen_NZ
dc.rights.holderAll rights, except those explicitly waived, are held by the Authoren_NZ
dc.rights.licenseAuthor Retains Copyrighten_NZ
dc.rights.urihttps://www.wgtn.ac.nz/library/about-us/policies-and-strategies/copyright-for-the-researcharchive
dc.subjectManganese compoundsen_NZ
dc.subjectOrganic compoundsen_NZ
dc.subjectAminesen_NZ
dc.titleThe Synthesis and Characterisation of Manganese Amine Complexesen_NZ
dc.typeTexten_NZ
thesis.degree.disciplineChemistryen_NZ
thesis.degree.grantorTe Herenga Waka—Victoria University of Wellingtonen_NZ
thesis.degree.levelDoctoralen_NZ
thesis.degree.nameDoctor of Philosophyen_NZ
vuwschema.type.vuwAwarded Doctoral Thesisen_NZ

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