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Synthesis of ionic boron amphiphilic diblock copolymers and pyridylborate ligands for transition metal complexes
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Title
Synthesis of ionic boron amphiphilic diblock copolymers and pyridylborate ligands for transition metal complexes
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ETD_2436
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http://hdl.rutgers.edu/1782.2/rucore10002600001.ETD.000052184
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eng
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theses
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Chemistry
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Topic
Diblock copolymers--Synthesis
Subject
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(authority = ETD-LCSH)
Topic
Ligands--Synthesis
Subject
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(authority = ETD-LCSH)
Topic
Transition metal complexes
Abstract
Atom transfer radical polymerization (ATRP) has been successfully used to prepare well-defined poly(trimethylsilyl)styrenes and the diblock copolymers, poly(trimethylsilyl)styrene-b-polystyrene, with controlled molecular weight and low polydispersity. Quantitative replacement of trimethylsilyl groups with boron tribromide in dichloromethane provided an important highly Lewis acidic intermediate that have allowed for the preparation of novel boron containing borate and boronium types of homopolymers and amphiphilic diblock copolymers with different post-polymerization modification processes. Characterizations including NMR spectroscopy, gel permeation chromatography (GPC) and the representative elemental analysis have been applied to confirm the quantitative transformations from the silylated polymers to the boron containing ionic polymers. The self-assembly properties in block selective solvents of the amphiphilic block copolymers were extensively studied. Most importantly, through an electro-static interaction, the weakly coordinating pentafluorophenyl borate block copolymers were successfully used to attach an organo-rhodium catalyst and then underwent self-assembly in selective solvent to give rise to transition metal containing micelles with well-defined nanostructures.
In the last chapter, synthesis and characterizations of a variety of novel multidentate pyridylborate ligands are described. An appropriate procedure for synthesis of 2-pyridyl magnesium chloride in a usual dimeric structure was developed. The 2-pyridyl magnesium chloride was then used to react with different arylbromoboranes in dichloromethane or toluene affording different multidentate ligands. The tris(2-pyridyl)borate ligands were the first pyridine based tripod ligands with a boron atom as the bridging head and their complexation with Fe(II) was studied by cyclic voltammetry (CV) and UV-vis spectroscopy. All the structures of the ligands and metal complexes were determined by single crystal X-ray spectroscopy. The styryltris(2-pyridyl)borate monomer was successfully polymerized in a free radical polymerization to give a polymer with good yield and high molecular weight. NMR analysis was used to confirm the formation of this novel polydentate polymer.
In the last chapter, synthesis and characterizations of a variety of novel multidentate pyridylborate ligands are described. An appropriate procedure for synthesis of 2-pyridyl magnesium chloride in a usual dimeric structure was developed. The 2-pyridyl magnesium chloride was then used to react with different arylbromoboranes in dichloromethane or toluene affording different multidentate ligands. The tris(2-pyridyl)borate ligands were the first pyridine based tripod ligands with a boron atom as the bridging head and their complexation with Fe(II) was studied by cyclic voltammetry (CV) and UV-vis spectroscopy. All the structures of the ligands and metal complexes were determined by single crystal X-ray spectroscopy. The styryltris(2-pyridyl)borate monomer was successfully polymerized in a free radical polymerization to give a polymer with good yield and high molecular weight. NMR analysis was used to confirm the formation of this novel polydentate polymer.
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electronic resource
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xxiv, 300 p. : ill.
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Ph.D.
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by Chengzhong Cui
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Cui
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Chengzhong
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1974-
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Chengzhong Cui
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Jaekle
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Frieder
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Frieder Jaekle
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Sheridan
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John
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John B. Sheridan
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Roger
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Roger Lalancette
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Sumerlin
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Brent
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Brent S. Sumerlin
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Rutgers University
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Graduate School - Newark
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2010
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2010-01
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xx
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Rutgers University Electronic Theses and Dissertations
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Graduate School - Newark Electronic Theses and Dissertations
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rucore10002600001
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doi:10.7282/T3DN4573
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ETD doctoral
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The author owns the copyright to this work.
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Copyright protected
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Open
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Cui
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Chengzhong
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2010-01-12 20:51:28
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Chengzhong Cui
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Rutgers University. Graduate School - Newark
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I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
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