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Title: Developing new routes to f-element heterometallic complexes
Author: Hickson, James
ISNI:       0000 0004 7659 1089
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2019
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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).
Supervisor: Farnaby, Joy ; Long, Nicholas Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral