DFT calculations on the interaction of phosphazenes with transition metals : a thesis presented in partial fulfillment of the requirements for the degree of Master of Science in Chemistry at Massey University, Palmerston North

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dc.contributor.authorDavidson, Ross James
dc.date.accessioned2009-07-20T02:59:05Z
dc.date.availableNO_RESTRICTIONen_US
dc.date.available2009-07-20T02:59:05Z
dc.date.issued2007
dc.description.abstractThe electronic structure of substituted cyclic phosphazenes has been investigated using Density Functional Theory (DFT) and Natural Bond Order (NBO) analysis. NBO analysis shows covalent, ionic and negative hyper-conjugation interactions all contribute to the electronic structure of cyclic phosphazenes. The geometric and electronic structural changes that occur when transition metals are coordinated to the nitrogen atom of the phosphazene ring have been analyzed using the NBO model. The bonding of transition metal ions with the ring nitrogen on the phosphazene was investigated by modeling hexakis(2-pyridyloxy)cyclotriphosphazene, hexakis(4-methyl-2-pyridyloxy)cyclotriphosphazene and octakis(2- pyridyloxy)cyclotetraphosphazene with different metal ions (Co(II), Ni(II), Cu(II), Zn(II)) in their assorted configurations with DFT as implemented in the Gaussian03 package. First-row transition metals bind to the phosphazene ring with simple s donor behaviour via the ring nitrogen. The lengthening of the PN bonds adjacent to the coordinated metal centre is a result of electron density being removed from the PN bonding orbitals and going into the 4s orbital of the metal ion. Investigating the pyridine substituents on the phosphazene ring showed that these can affect the PN bonds in a similar fashion, although weaker, to the transition metals. This effect is the result of the pyridine nitrogen lone pair affecting the negative hyperconjugation component of the PN bond. Coupling between two metal atoms coordinated to the phosphazene ring was investigated by DFT calculations, which showed molecular orbitals in both the tricyclic and tetracyclic phosphazene capable of providing an ‘electron density bridge’ between the metal centres. These results are in accord with ESR and magnetic susceptibility results, which can be explained in terms of weak antiferromagnetic coupling between metal ions. The cyclic phosphazenes are model compounds for polyphosphazenes and the results obtained from this work will provide insight into the electronic properties of this important class of inorganic polymers.en_US
dc.identifier.urihttp://hdl.handle.net/10179/937
dc.language.isoenen_US
dc.publisherMassey Universityen_US
dc.rightsThe Authoren_US
dc.subjectPhosphazenesen_US
dc.subjectTransition metalsen_US
dc.subject.otherFields of Research::250000 Chemical Sciences::250200 Inorganic Chemistry::250201 Transition metal chemistryen_US
dc.titleDFT calculations on the interaction of phosphazenes with transition metals : a thesis presented in partial fulfillment of the requirements for the degree of Master of Science in Chemistry at Massey University, Palmerston Northen_US
dc.typeThesisen_US
massey.contributor.authorDavidson, Ross James
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorMassey Universityen_US
thesis.degree.levelMastersen_US
thesis.degree.nameMaster of Science (M.Sc.)en_US
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