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Title: Crystallographic and modelling studies of transition metal complexes
Author: Parkin, Andrew
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2002
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Molecular mechanics techniques have been applied to the investigation of the formation of transition metal complexes. In addition to the determination of many relevant crystal structures, the two major projects carried out were: a) molecular structures within the crystalline forms of copper(I) ligated by phosphine and alkoxide or aryloxide ligands, and b) modes of extraction of salicylaldimine derivatives for metal salt transport. Copper(I) is observed to crystallise with phosphine and alkoxide or aryloxide ligands in five different structural motifs. The formation of these structural motifs was rationalised in terms of electronic and steric effects. Electronic effects were approximated to the pKa of the alkoxide or aryloxide ligand. Steric effects were modelled using molecular mechanics calculations. Parameters for molecular mechanics were obtained from the Cambridge Structural Database. The results show that the formation of molecular structures can indeed be justified this way, and some structures have been predicted. Recently White and Tasker have proposed a novel method of "metal salt" extraction based on derivatives of the salicylaldimine ligand. The addition of pendant tertiary amines to this ligand allows the encapsulation of an anion, and thus transport of the entire "metal salt". This has been particularly successful for square planar copper(II) salts. Molecular mechanics calculations were employed to model the possible structures formed in the solution species to aid design of improved extractants for nickel(II). Parameters for molecular mechanics were obtained from the Cambridge Structural Database. The results enabled rationalisation of the poor performance of the original design, and the design of species with improved geometries for anion encapsulation.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available