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 Award | 1 Aug 2021 |
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Original language | English |
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Awarding Institution | - The University of Manchester
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Supervisor | Stephen Liddle (Supervisor) & David Mills (Supervisor) |
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Synthesis and Characterisation of f-Block Silanide Complexes
Reant, B. (Author). 1 Aug 2021
Student thesis: Phd