Structure and bonding in transition metal complexes
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
The work described in this thesis is grouped into two main parts. Part 1 is concerned with the structural chemistry of rhenium and technetium; part 2 with the investigation of a distorted tetrahedral copper (II) complex. The structure of TcCl₄ has been shown to contain one-dimensional polymeric units in which each technetium atom has a distorted octahedral to six chlorine atoms. There is not metal-metal bridging and the structure differs from that of ReCl₄. The structure of a complex once thought to contain the dimeric Tc₂OCl₁₀⁴- ion has been studied, and shown to contain, instead, the monomeric Tc(OH)Cl₅²- ion. The crystal structure determination of a trinuclear rhenium (III) species, CsRe₃Br₇Cl₃(H₂O)₂, is presented. This is the first “mixed halide” trinuclear complex of Re (III) to be studied. The final refinement of the Cs₂Re₃Br₁₁ structure discussed, and correlated with previously determined structures. Part 2 presents the structure determination of bis-(dipyrromethene) Copper (II), found to contain Cu in a considerably distorted tetrahedral configuration. The structural data is compared with that found in other distorted tetrahedral Cu complexes. The routine computational methods common to each of the five structure determinations have been described in a final chapter to avoid needless repetition. Tables not essential to the text have been collected in the Appendices.