eprintid: 1559959
rev_number: 29
eprint_status: archive
userid: 608
dir: disk0/01/55/99/59
datestamp: 2017-10-06 07:57:07
lastmod: 2020-07-03 03:01:25
status_changed: 2017-10-06 07:57:07
type: thesis
metadata_visibility: show
creators_name: Mountain, ARE
title: Quantum Chemical Modelling of Organo Transition Metal Structure, Bonding, and Reaction Mechanism
ispublished: unpub
divisions: UCL
divisions: A01
divisions: B04
divisions: C06
abstract: In this thesis, density functional theory is used to investigate the structure, bonding, and reaction mechanisms of two families of organometallic compounds discussed below. The first chapter briefly introduces the research projects undertaken for this PhD, while the second introduces the theoretical background of electronic structure calculations.
Chapter 3 begins with an introduction to homogenous Ziegler-Natta catalysis of olefin polymerisation, with a focus on chain propagation and termination reaction mechanisms for propylene homopolymerisation. These mechanisms are then explored in benchmarking studies of the naked cationic post-metallocene catalyst [MeTiCp*{CN(Ph)N(iPr)2}]+, comparing reaction profiles calculated using different approaches to describe dispersion and solvent effects, as well as those found using ab initio methods. It is concluded that dispersion interactions play an important role in predicting the expected trends in reaction barrier height for propagation vs. termination, and the methodology which best describes this is chosen and implemented in the subsequent chapter.
The effects of the anionic co-catalyst [B(C6F5)4] on homopolymerisation studies of ethylene and propylene with [MeTiCp*{CN(Ph)N(iPr)2}]+, are explored in Chapter 4. Differences between olefin complexation, chain propagation and termination reactions calculated with and without the anion are discussed, as well as predictions of macroscopic properties of polymers produced using this catalytic system.
Chapter 5 introduces a different research project;	the investigation of
the structure, bonding, and reactivity of metal boryl and gallyl compounds, Ln{E(NArCH)2}{Me3SiCH2C(NCy)2}2(THF)n (Ln = Sc, Y, Lu; E = B, Ga; n = 0, 1). The changes in structure and Ln–E bonding interaction are compared between five- and six-coordinate analogues of the systems, accounting for the difference in coordination number of the boryls vs. the gallyls, and their reactivity with carbodiimide iPrNCNiPr. Finally, the mechanism for carbodiimide insertion into the Mg–Ga bond of Mg{'iPPNacNac}Ga(NDippCH)2} systems is explored.
date: 2017-06-28
date_type: published
oa_status: green
full_text_type: other
thesis_class: doctoral_open
language: eng
thesis_view: UCL_Thesis
primo: open
primo_central: open_green
verified: verified_manual
elements_id: 1299169
lyricists_name: Mountain, Abigail
lyricists_id: AREMO87
actors_name: Mountain, Abigail
actors_id: AREMO87
actors_role: owner
full_text_status: public
pages: 197
event_title: University College London
institution: UCL (University College London)
department: Chemistry
thesis_type: Doctoral
citation:        Mountain, ARE;      (2017)    Quantum Chemical Modelling of Organo Transition Metal Structure, Bonding, and Reaction Mechanism.                   Doctoral thesis , UCL (University College London).     Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/1559959/1/AREMountainThesisFinal.pdf