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UBC Theses and Dissertations

The synthesis and characterization of some molybdenum, rhenium and rhodium complexes incorporating pyrazolylgallate ligands Cooper, David Arthur


Several uninegative ligands based on a gallium core and incorporating pyrazolyl groups have been synthesized and their metathesis reactions with molybdenum, rhenium and rhodium halides have been studied. The bidentate pyrazolylgallate ligand [formula omitted] has been incorporated in the complexes [formula omitted]. The unsymmetric tridentate pyrazolylgallate ligands [formula omitted] display a variable reactivity towards molybdenum, rhenium and rhodium precursors. Although no complexes incorporating L⁴ were isolated, L₂ and L₃ were shown to co-ordinate facially in the octahedral complexes [formula omitted] and [formula omitted]. In addition, a meridional co-ordination geometry of L₂ has been structurally characterized in the square planar rhodium(I) complex, L₂Rh(CO). This co-ordinatively unsaturated rhodium(I) species was shown to undergo an interesting oxidative addition reaction with methyl iodide followed by a methyl migration reaction to give a rhodium(III) acetyl derivative. Less predictable products have also been obtained in this study; these include the dimeric species [formula omitted] formed from the reaction of NaL₃ with [formula omitted] and also an unexpected chlorine-containing complex, [formula omitted] from the reaction of [formula omitted]. [formula omitted] the product of the reaction between [formula omitted]. [Formula omitted] (the precursor of Ld) has been structurally shown to possess a novel eight-membered Ga-(N-C-S)₂-Ga ring.

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