1,3-N,O-Chelated early-transition-metal complexes for the activation and formation of C−E (E = H, C, N, O) bonds
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Griffin, Samuel Elliot
issued: 2023-09-30T07:00:00Z
issued: 2021
related degree: Doctor of Philosophy - PhD
degree grantor: University of British Columbia
description: This thesis describes the exploration of 1,3-N,O-chelated early-transition metals and their applications in diverse catalytic reactions. While cyclopentadienyl-ligated metal complexes and their derivatives are highly robust and have found extensive catalytic applications in industry, their robustness limits their ability to act cooperatively with the metal centre to promote new and challenging transformations. In addition, the multi-step synthetic routes required to access modified cyclopentadienyl derivatives hinder tuning of the steric and electronic properties as needed. 1,3-N,O-chelating ligands are complementary to cyclopentadienyl ligands as a result of their highly modular syntheses and unsymmetrical donor properties, leading to flexible coordination modes, hemilability, and potential for metal-ligand cooperativity. However, 1,3-N,O-chelating ligands are comparatively underexplored despite promising recent advances in catalysis. Chapter 2 describes the use of zirconium ureate complexes for the catalytic hydroamination of 2-vinylpyridine. Stoichiometric and mechanistic studies revealed that the reaction with 2-vinylpyridine proceeds through an aza-Michael mechanism, where the C−N bond forming step is reversible and can be directly observed by variable temperature 1H NMR spectroscopy. In Chapter 3, these zirconium ureate complexes were investigated for their reactivity in hydroaminoalkylation. This led to the discovery of the first catalytic example of hydroaminoalkylation with alkyne substrates to directly access allylic amines. Stoichiometric and mechanistic studies suggest that the open coordination sphere of the zirconium catalyst aids in promoting the challenging reaction steps necessary for catalytic turnover. Chapter 4 investigates the coordination chemistry and reactivity of vanadium pyridonate complexes, which were previously unexplored. These compounds can be made easily via protonolysis of amido or organometallic starting materials, as is the case fo…
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/79049
note: 1,3-N,O-Chelated Early-Transition-Metal Complexes for the Activation and Formation of C−E (E = H, C, N, O) Bonds by Samuel Elliot Griffin B.Sc. (Hons.), The University of British Columbia Okanagan, 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) July 2021 © Samuel Elliot Griffin, 2021 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, the dissertation entitled: 1,3-N,O-Chelated Early-Transition-Metal Complexes for the Activation and Formation of C−E (E = H, C, N, O) Bonds submitted by Samuel Elliot Griffin in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Examining Committee: Laurel L. Schafer, Professor, Chemistry, UBC Supervisor Parisa Mehrkhodavandi, Professor, Chemistry, UBC Supervisory Committee Member Michael O. Wolf, Professor, Chemistry, UBC University Examiner Gren N. Patey, Professor, Chemistry, UBC University Examiner Warren E. Piers, Professor, Chemistry, University of Calgary External Examiner Additional Supervisory Committee Members: Harry Brumer, Professor, Chemistry and Michael Smith Laboratories, UBC Supervisory Committee Member Pierre Kennepohl, Professor, Chemistry, UBC Supervisory Committee Member iii Abstract This thesis describes the exploration of 1,3-N,O-chelated early-transition metals and their applications in diverse catalytic reactions. While cyclopentadienyl-ligated metal complexes and their derivatives are highly robust and have found extensive catalytic applications in industry, their robustness limits their ability to act cooperatively with the metal centre to promote new and challenging transformations. In addition, the multi-step synthetic routes required to access modified cyclopentadienyl derivatives hinder tuning of the steric and e…
has type: Thesis/Dissertation
date issued: 2021-11
is shown at: 10.14288/1.0400465
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: Schafer, Laurel
type: Text
identifier URI: http://hdl.handle.net/2429/79049