Item – Theses Canada

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OCLC number
1032935539
Link(s) to full text
LAC copy
Author
Tan, Runyu.
Title
Exploring Quinoline and Pyridine Functionalized Binucleating Ligands : Syntheses, Complexation and Reactivity.
Degree
Ph. D. -- University of Toronto, 2011
Publisher
Toronto : University of Toronto, 2011.
Description
1 online resource
Notes
Includes bibliographical references.
Abstract
The objective of this thesis is to explore quinoline and pyridine functionalized multidentate ligand systems that are capable of accommodating two metal species and to study the reactivity of the resulting bimetallic complexes, in the aim of investigating potential synergistic effects between the metal centres. A series of functionalized 1,2,4,5-tetrakis(quinolin-8-yl)benzene ligands were synthesized. The dinuclear platinum complexes of these ligands could activate C-Cl bonds of chlorinated solvents and dearomatize the central benzene ring of the ligand concurrently. A series of extended ligands where the central benzene ring was replaced by trans-stilbene, diphenylacetylene and pyrene groups were synthesized in order to explore more ligand-based reactivity. Two dinuclear diphenylplatinum complexes were synthesized. A series of mono- and bis-quinolinyl functionalized thiophene ligands have also been synthesized. Dinuclear platinum complexes of the bisquinolinyl thiophenes were isolated, which represented the first group 10 metal complexes of η2-thiophene, a long sought-after intermediate relevant to the hydrodesulfurization (HDS) process. Oxidation of these diplatinum complexes by MeOTf led to the isolation of mononuclear chiral five-coordinate platinum(IV) complexes, and a ligand twisting mechanism of these complexes was proposed on the basis of dynamic NMR studies and DFT calculations to elucidate the interconversion of two enantiomers. The reactions of monoquinolinyl functionalized thiophenes and [Pt(CH3)2(SMe2)]2/[PtH(dippe)]2 led to selective C-H/C-S bonds activation of the thiophene moieties respectively. A luminescent U-shaped bis-dipyridylamine functionalized anthracene ligand was designed and synthesized. This compound was fabricated into OLED devices and shown to be a promising emissive material. As a ligand, it adopted different coordination modes, acting as either binucleating double bidentate ligand, or mononucleating tetradentate ligand. Three dirhodium, dizinc and monozinc complexes were synthesized. Pyridine and phosphine functionalized 4,5-diazafluorene ligands were synthesized and the former ligand served as a mononucleating ligand via the two nitrogen donor atoms of the diazafluorenyl moiety while the latter ligand could act as a binucleating ligand via the phosphorus donor atom, two nitrogen donor atoms and the carbon donor atom. Several Ru, Rh, Pt, Cu and Au complexes were synthesized, and two Pt-Pt, Pt-Cu bimetallic complexes were isolated and characterized based on the phosphine functionalized ligand.
Other link(s)
hdl.handle.net
tspace.library.utoronto.ca
Subject
inorganic chemistry.
organometallic chemistry.
0488.