Supramolecular chemistry of palladium and platinum-containing macrocycles : from ring-expansion to host-guest complexes
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Carta, Veronica
issued: 2023-04-30T07:00:00Z
issued: 2018
related degree: Doctor of Philosophy - PhD
degree grantor: University of British Columbia
description: Two main projects are presented in this thesis. In the first project we used ligand exchange to influence the reactivity of an unstrained palladium-containing metallomacrocycle toward ring-opening metathesis polymerization (ROMP) reaction. The ligand-exchange rate on the palladium center between acetonitrile and six different ligands was investigated for an NNN pincer bis(amido)pyridine metallomacrocycle and compared with its corresponding open form. Kinetic studies showed that the small size of the macrocycle cavity impedes ligand exchange. We then used a bulky ligand (2,6-lutidine) to provide steric hindrance, blocking ring-closing and favouring ROMP of the NNN pincer bis(amido)pyridine metallomacrocycle. The second project involves the synthesis and characterization of several Pt²âº, Pt³âº, and Ptâ´âº phenylpyridine complexes. We first used a bidentate functionalized phenylpyridine ligand, then two flexible tetradentate ligands featuring an ethylene glycol chain, and finally two preorganized tetradentate ligands, one of which contained a full crown ether functionality. The presence of the crown ether functionality makes these compounds attractive for host-guest chemistry applications. The synthetic challenges related to obtaining biscyclometalated platinum monomeric complexes with phenylpyridine-containing ligands were addressed by using different approaches: high dilution, cation coordination, and ligand preorganization. Some of the complexes prepared appear to be promising for cation recognition and for the formation of supramolecular assemblies such as rotaxanes and pseudorotaxanes.
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/67707
note: SUPRAMOLECULAR CHEMISTRY OF PALLADIUM AND PLATINUM-CONTAINING MACROCYCLES: FROM RING-EXPANSION TO HOST-GUEST COMPLEXES by Veronica Carta MSc., Sapienza Università di Roma, 2012 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) October 2018 © Veronica Carta, 2018 ii The following individuals certify that they have read, and recommend to the Faculty of Graduate and Postdoctoral Studies for acceptance, the dissertation entitled: Supramolecular chemistry of palladium and platinum-containing macrocycles: from ring-expansion to host-guest complexes submitted by Veronica Carta in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Examining Committee: Mark MacLachlan Supervisor Michael Fryzuk Supervisory Committee Member Supervisory Committee Member Jennifer Love University Examiner Alexander Wang University Examiner Additional Supervisory Committee Members: Russ Algar Supervisory Committee Member Parisa Mehrkhodavandi Supervisory Committee Member !iii Abstract Two main projects are presented in this thesis. In the first project we used ligand exchange to influence the reactivity of an unstrained palladium-containing metallomacrocycle toward ring-opening metathesis polymerization (ROMP) reaction. The ligand-exchange rate on the palladium center between acetonitrile and six different ligands was investigated for an NNN pincer bis(amido)pyridine metallomacrocycle and compared with its corresponding open form. Kinetic studies showed that the small size of the macrocycle cavity impedes ligand exchange. We then used a bulky ligand (2,6-lutidine) to provide steric hindrance, blocking ring-closing and favouring ROMP of the NNN pincer bis(amido)pyridine metallomacrocycle. The second project involves the synthesis and characterization of several Pt2+, Pt3+, and Pt4+ phenylpyridine c…
has type: Thesis/Dissertation
date issued: 2019-02
is shown at: 10.14288/1.0373100
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
type: Text
identifier URI: http://hdl.handle.net/2429/67707