Chemistry of β-diketiminate Group 14 and Group 2 complexes and macrocyclic amines and amine ethers

Taylor, Morgan James (2012) Chemistry of β-diketiminate Group 14 and Group 2 complexes and macrocyclic amines and amine ethers. Doctoral thesis (DPhil), University of Sussex.

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Abstract

Group 14 metal(II) alkyl complexes are very rare, with few examples being studied in
great detail. To this end, a series of β-diketiminate lead(II) alkyl and aryl complexes,
[{(2,6-iPr2C6H3)NC(CH3)}2CH]PbR (R = Me, iPr, sBu, Np, Bn, tBu and Ph) were
synthesised and a number of computational studies were performed on them to increase
the understanding of the nature of these compounds. Reactivity studies on both the lead,
and the analogous tin systems, showed that they could be used as precursors to generate
examples of very rare two-coordinate group 14 metal cation complexes, including the
first example of a β-diketiminate two-coordinate lead(II) cation, and an analogous
example of a rare low-coordinate tin(II) system. These were studied in detail by
computational methods, including the stabilising effects of a coordinated solvent
molecule on the metal centre.

β-Diketiminate magnesium alkyl complexes were generated to investigate the +2
oxidation state metal environment without the presence of a stereochemically active
lone pair, as present in the group 14 metal(II) complexes. A carbodiimide was
successfully inserted into the magnesium-carbon bond, and novel magnesium
phosphides were generated from the alkyl complexes. Solvent stabilisation effects on
these phosphides were also studied by computational methods.

A series of macrocyclic amines and amine ethers were synthesised to investigate the
hydrolysis of a phosphate diester model RNA system by lead(II) salts, monitored by
UV-visible kinetics. The reaction kinetics gave no reproducible results, but the
syntheses of the macrocycles are presented in detail for further citation.

Item Type: Thesis (Doctoral)
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0241 Organic chemistry
Depositing User: Library Cataloguing
Date Deposited: 20 Jun 2012 07:52
Last Modified: 04 Sep 2015 13:16
URI: http://sro.sussex.ac.uk/id/eprint/39640

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