The effect of ligand structure on the reactivity of a diverse group of aqua-hydroxytetraazacobalt(III) complexes towards the hydrolysis of phosphate diesters and carboxylic esters has been investigated. It has been shown that the magnitude of the N-Co-N bond angle that lies opposite to the aqua-hydroxy ligands is influential in determining which complexes are best able to stabilize a strained four-membered ring, and this has been related to the relative rates at which these complexes promote reactions involving four-membered ring formation. The great range of rates of acid catalyzed decarboxylation of the carbonato derivatives of these complexes has been explained in terms of the same ligand-effect, and a correlation between the rate of this reaction and Co(III) aqua-hydroxy promoted phosphate diester hydrolysis and carboxylic ester hydrolysis has been established. / The relationship between reactivity of a complex towards phosphate diester hydrolysis and mode of binding of inorganic phosphate has been elucidated. / The true catalysis of methyl acetate hydrolysis by the two complexes ((13aneN$ sb4)$Co(OH)(OH$ sb2)$) $ sp{2+}$ and ((cyclen)Co(OH)(OH$ sb2)$) $ sp{2+}$ has been demonstrated, it has been shown that complexes which are capable of this kind of catalysis can bind acetate as a chelate.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.39231 |
| Date | January 1990 |
| Creators | Moore, Andrew |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001170714, proquestno: NN66405, Theses scanned by UMI/ProQuest. |
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