Synthesis and Characterisation of f-Block Silanide Complexes

  • Benjamin Reant

Student thesis: Phd

Abstract

The chemistry of f-block silanides has seen a slow but steady increase since its inception in the 1980s, and the field is immature compared to the well-developed carbon chemistry of the f-block. Development of this field will allow researchers to perform in-depth analysis of the bonding and properties of M-Si linkages and to explore new opportunities for applications, for example in catalysis and nuclear fuel technologies. The area of f-block silicon chemistry, along with the heavier tetrels has been reviewed in paper one. Herein, this work presents the synthesis and characterisation of analogous thorium and uranium silanide complexes, [An(Cp')3{Si(SiMe3)3}] (An = Th, U; Cp' = {C5H4SiMe3}), marking the first structurally authenticated example of a thorium silanide complex, paper two. The expansion of f-element silicon chemistry to trialkylsilanide ligands, in a field dominated by tris(trimethylsilyl)silanide, provided new M(II)-Si complexes, [M(SitBu3)2(THF)y] (M = Mg, Ca, Yb, y = 2; M = Sm, Eu, y = 3) and [M(SitBu2Me)2(THF)y] (M = Mg, y = 2; M = Ca, Sm, Eu, Yb, y = 3); we correlated 29Si NMR spectroscopy with DFT calculations to evaluate covalency in these systems, finding significant trends, paper three. Finally we report an isostructural series of early d- and f-block silanide complexes, [M(Cp'')2{Si(SiMe3)3}] (M = Ti, Zr, La, Ce, Nd, U; Cp'' = {C5H3(SiMe3)2-1,3}), and describe our initial characterisation of them and their electronic configurations using optical spectroscopy, continuous wave EPR spectroscopy, magnetism and CASSCF calculations, paper four.
Date of Award1 Aug 2021
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorStephen Liddle (Supervisor) & David Mills (Supervisor)

Keywords

  • Silicon
  • Chemistry
  • Actinide

Cite this

'