Russo, Maria Rosa; (2002) Quantum mechanical and synthetic studies of coordination and organometallic complexes of lanthanides and other heavy metals. Doctoral thesis (Ph.D), UCL (University College London).

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Abstract

This thesis presents an investigation of the structure and bonding of heavy element complexes. In particular, the thesis contains computational analyses of the steric and electronic factors influencing the structure and bonding of complexes containing the lanthanides or other heavy metals. In addition the thesis presents synthetic investigations related to some of these computational issues. Density Functional Theory, with the inclusion of scalar-relativistic corrections, has been used to investigate the bonding of Lanthanides and other heavy metals in a series of complexes with ligands ranging from polihapto-π-donors such as cyclopentadienyls, to monodentate σ-bonding ligands such as chalcogenolates and cyanides. These calculations provide a rationalization of the previously proposed/determined geometries of [(CN)₅PtTl(CN)n]ⁿ⁻ (chapter 3) and lanthanide chalcogenolates (chapter 4). These latter studies provide a detailed insight into the nature and bonding of lanthanide metals and allow rationalization of observed structural features in simple electrostatic terms. Chapter 5 describes laboratory experiments aimed at the preparation of lanthanide complexes containing 1,3 dialkylated calix[4]arenes as ancillaries. Spectroscopic and structural evidence for a number of complexes is presented together with several attempts to develop improved starting materials for lanthanide chemistry including alkyl, aryls and amides.

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