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