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Title: Synthesis and properties of early metal bulky silylamide complexes
Author: Goodwin, Conrad
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2017
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Silylamide ligands have been used throughout the Periodic Table since the 1960s. They have delivered landmark complexes by providing the first three co-ordinate f-element complexes, the first trigonal planar f-element complexes and the first near-linear f-element complexes. This area is reviewed in Chapter 2.Herein, this work presents the first uses of several novel bis-silylamide ligands developed at Manchester which take the form {N(SiR3)2} where R = Me, iPr or tBu to afford four novel ligands: N ʹ, {N(SiMe3)(SiiPr3)}; N**, {N(SitBuMe2)2}; N* {N(SitBuMe2)(SiiPr3)}; and N , {N(SiiPr3)2}. Group 1 and 2 complexes of all of these ligands are presented along with the previously reported N*ʹ [N*ʹ = {N(SitBuMe2)(SiMe3)}]; which show variable bonding motifs based on the steric bulk. The N** and N ligands have formed the bulk of the work presented and were used to stabilise the first trigonal planar actinide complex [U(N**)3], as well as the first near-linear Ln(II) (Ln = lanthanide) complexes [Ln(N )2] (Ln = Sm, Eu, Yb, Tm). Additionally the trigonal planar Ln(II) complexes [K(2.2.2-cryptand)][Ln(N**)3] (Ln = Sm, Eu, Yb, Tm) have also been synthesised to compare the physicochemical properties of trigonal planar and near-linear geometries on the same elements with similar ligands.
Supervisor: Natrajan, Louise ; Mills, David Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: SMM ; Single Molecule Magnet ; Near-linear ; Trigonal Planar ; Actinide ; Early Metal ; Lanthanide ; Silylamide