Synthesis and Properties of Early Metal Bulky Silylamide Complexes

Student thesis: Phd


Synthesis and Properties of Early Metal Bulky Silylamide Complexes: A thesis submitted to The University of Manchester for the degree of Doctor of Philosophy in the Faculty of Science and Engineering.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.
Date of Award31 Dec 2017
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorLouise Natrajan (Supervisor) & David Mills (Supervisor)


  • Single Molecule Magnet
  • SMM
  • Near-linear
  • Trigonal Planar
  • Actinide
  • Early Metal
  • Lanthanide
  • Silylamide

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