Modeling the polymerization of 1-phosphaisoprene : explorations of the synthesis and reactivity of 1-phosphabutadienes
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Walsgrove, Henry
issued: 2025-05-31T07:00:00Z
issued: 2023
related degree: Doctor of Philosophy - PhD
degree grantor: University of British Columbia
description: The investigation of macromolecules containing phosphorus(III) atoms is an active area of research due to the functionality imparted by the heteroatom. Additionally, molecular Pᶦᶦᶦ-compounds are pervasive in synthetic chemistry due to their use as ligands for metal centers. This thesis outlines the investigation of the reactivity of a unique class of low-coordinate Pᶦᶦᶦ-compounds, 1-phosphabutadienes (P=C−C=C), which are phosphorus-containing analogues of organic butadienes. Chapter 1 acquaints the reader with the background and functionality of unique low-coordinate phosphorus compounds. An in-depth examination of the prior art in the polymerization, cyclization and coordination chemistries of these compounds is provided. Chapter 2 focuses on the anionic polymerization of 1-phosphaisoprene [Mes*P=C(Me)−CH=CH₂; Mes* = 2,4,6-tri-t-butylphenyl] to furnish poly(1-phosphaisoprene). Molecular model studies including isolation of the propagating anion and models displaying both 4,3- and trans-4,1-enchainment are presented. The structural data gained from these molecular models are placed into the context of the microstructure of poly(1-phosphaisoprene). Chapter 3 reports the reaction of poly(1-phosphaisoprene) with [Pd(cod)Cl₂] and [Pd(η³-C₃H₅)(μ-Cl)]₂. It is shown that a concentrated solution of the former can undergo reversible gelation. The gelation does not occur upon treatment of poly(1-phosphaisoprene) with [Pd(η³-C₃H₅)(µ-Cl)]₂, indicating that cross-linking within the polymer network is responsible for gel formation. The study is complemented with molecular models. Chapter 4 focuses on cyclization reactions of 1-phosphabutadienes. Specifically, a [4+2] adduct of 1-phosphaisoprene with unique regiochemistry is disclosed and the observed reactivity is complemented by DFT calculations. Furthermore, the synthesis and [2+2] cyclization of a novel 1-phosphabutadiene, Mes*P=C(Me)−C(Me)=CH₂, is reported. Chapter 5 focuses on the synthesis and characterization of Mes*P=C(Si…
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/84549
note: Modeling the Polymerization of 1-Phosphaisoprene: Explorations of the Synthesis and Reactivity of 1-Phosphabutadienes by Henry Walsgrove MSci., The University of Nottingham, 2016 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE AND POSTDOCTORAL STUDIES (Chemistry) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) April 2023 © Henry Walsgrove, 2023 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, the dissertation entitled: Modeling the Polymerization of 1-Phospahisoprene: Explorations of the Synthesis and Reactivity of 1-Phosphabutadienes submitted by Henry Walsgrove in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry Examining Committee: Derek Gates, Professor, Chemistry, UBC Supervisor Mark MacLachlan, Professor, Chemistry, UBC Supervisory Committee Member Andrew MacFarlane, Professor, Chemistry, UBC University Examiner Zac Hudson, Associate Professor, Chemistry, UBC University Examiner Additional Supervisory Committee Members: Pierre Kennepohl, Professor, Chemistry, University of Calgary Supervisory Committee Member Martin Tanner, Professor, Chemistry, UBC Supervisory Committee Member iii Abstract The investigation of macromolecules containing phosphorus(III) atoms is an active area of research due to the functionality imparted by the heteroatom. Additionally, molecular PIII-compounds are pervasive in synthetic chemistry due to their use as ligands for metal centers. This thesis outlines the investigation of the reactivity of a unique class of low-coordinate PIII-compounds, 1-phosphabutadienes (P=C−C=C), which are phosphorus-containing analogues of organic butadienes. Chapter 1 acquaints the reader with the background and functionality of unique low-coordinate phosphorus compounds. An in-depth examination of the prior art in the polymerization, cyclization an…
has type: Thesis/Dissertation
date issued: 2023-11
is shown at: 10.14288/1.0431596
language: eng
degree discipline: Chemistry
provider: Vancouver : University of British Columbia Library
publisher: University of British Columbia
rights: Attribution-NonCommercial-NoDerivatives 4.0 International
rights URI: http://creativecommons.org/licenses/by-nc-nd/4.0/
scholar level: Graduate
contributor: Gates, Derek P.
type: Text
identifier URI: http://hdl.handle.net/2429/84549