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Title: Binuclear and polynuclear metal complexes with bulky ligands
Author: Graham, A.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2001
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This thesis presents routes to transition metal complexes of pyridonate and carboxylate ligands. Low nuclearity complexes with triphenyl acetate and 1st row transition metals of the formula [M4(OMe)4(O2CCPh3)4(MeOH)4] (M = Co, Ni or Zn) have been synthesised and mark a change from reactions with other carboxylates which produce linear trinuclear complexes. Molecular modelling studies investigate the close contacts that arise if triphenyl acetate is incorporated into a linear trinuclear compound to establish whether steric interactions are controlling reactivity. High nuclearity complexes with cobalt and nickel have been, made, many of which extend the range of complexes in which the metal atoms form a centred tricapped trigonal prism. These complexes all contain [M10(OH)6(O2CCPh3)6(xhp)6]2+ (xhp = a pyridone anion substituted at the six position) core with metal atoms capping the triangular faces of the centred prism. A variant on previous trapped trigonal prisms is also presented, in which the cap metal atoms cap the prism edges. In other complexes the metal atoms form new topologies, ranging from hexa- to octanuclear. In some complexes sodium atoms are also incorporated into the polynuclear cages. Reaction conditions for formation of these cages was investigated. Variation of the metal salt from chloride to nitrate influences both the yield of high nuclearity complexes and the timescale over which they are formed. The choice of recrystallisation solvent affects the cage formed. For example. hexanuclear and heterometallic octanuclear cobalt complexes follow identical syntheses except for the recrystallisation solvent. The means by which counterion and recrystallisation solvent influence reactivity is unclear.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available