Developing new routes to f-element heterometallic complexes
File(s)
Author(s)
Hickson, James
Type
Thesis
Abstract
An introduction to the significance of f-elements and heterometallic complexes is presented in Chapter 1. Chapter 2 takes the redox active ligand 1,10-phenanthroline-5,6-dione (pd) and explores its rare earth chemistry. It also develops a modular route to the preparation of the ternary lanthanide complexes [Ln(hfac)3(N,N′-pd)] (Ln = Y, Sc, La. hfac = 1,1,1-5,5,5-hexafluroacetylacetonate). Chapter 3 takes these complexes in oxidative addition reactions with vanadocenes, and describes the preparation of the lanthanide-vanadium(IV) heterobimetallic complexes [Ln(hfac)3(N,N′-O,O′-pd)VCpR2] (Ln = Y, Sc, La. CpR = Cp, CpMe4), as well as their electronic structure using a range of spectroscopic techniques and DFT calculations. Chapter 4 builds on this chemistry by using cobaltocene; the reaction between pd and CoCp2 leads to the isolation and full characterisation of the first 1,10-phenanthroline-5,6-semiquinone (pd•-) species, [CoCp2]+[pd]•-, via one electron reduction. Chapter 5 details other attempts at the one electron reduction at pd using a range of transition metal precursors. The attempted synthesis of a potassium pd salt is also described. Chapter 6 investigates the electron transfer reactivity between YX3 (X = OTf, Cl, I, hfac) precursors, pd and ferrocene, as well as describing the synthesis of the heteroleptic complexes [Y(hfac)2(OTf)(thf)3] and [La(hfac)(κ-OTf)(thf)2]. Chapter 7 is a preliminary study of the reactivity between pd and organometallic Ln(II) precursors such as [{(N{SiMe3}2)2(thf)Y}2(μ-η2:η2-N2)] or LnI2 (Ln = Sm, Dy).
Version
Open Access
Date Issued
2018-09
Date Awarded
2019-03
Copyright Statement
Creative Commons Attribution NonCommercial No Derivatives licence
Advisor
Farnaby, Joy
Long, Nicholas
Publisher Department
Chemistry
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)