Structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2007
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| Online Access: | http://hdl.handle.net/1721.1/39676 |
| _version_ | 1826194494045814784 |
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| author | Barder, Timothy E |
| author2 | Stephen L. Buchwald. |
| author_facet | Stephen L. Buchwald. Barder, Timothy E |
| author_sort | Barder, Timothy E |
| collection | MIT |
| description | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007. |
| first_indexed | 2024-09-23T09:56:40Z |
| format | Thesis |
| id | mit-1721.1/39676 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T09:56:40Z |
| publishDate | 2007 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/396762019-04-12T14:05:36Z Structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines Barder, Timothy E Stephen L. Buchwald. Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Dept. of Chemistry. Chemistry. Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007. This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections. Vita. Includes bibliographical references. Pd-catalyzed cross-coupling processes have become one of the most important and useful class of transformations in organic synthesis in the past 25 years. Supporting ligand design has been crucial in developing more effective catalysts. One highly effective class of ligand is that of biaryl phosphines. Herein are presented experimental and theoretical structural data on this class of phosphine that aids in elucidating what aspects of ligand architecture are beneficial for catalyst stability and reactivity. Additionally, examples of traditionally difficult Suzuki-Miyaura reactions are presented along with a fluorescent sensor that can be used to monitor boronic acid consumption in Suzuki-Miyaura reactions in situ. Finally, a rationale behind the resistance of dialkylbiaryl phosphines toward oxidation by molecular oxidation is described. Chapter 1. Expansion of the Suzuki-Miyaura Coupling Reaction. Chapter 2. X-Ray Crystal Structures of Biaryl Phosphine Pd(0) and Pd(II) Complexes. Chapter 3. Structural Insights into Active Catalyst Structures and Oxidative Addition to Biaryl Phosphine-Palladium Complexes via Density Functional Theory and Experimental Studies. (cont.) Chapter 4. Structural Insights into Amine Binding to Biaryl Phosphine-Palladium Complexes via Density Functional Theory and Experimental Studies. Chapter 5. Experimental and Theoretical Analysis of an Arene/Phosphine Ligated Pd(I) Dimer. Chapter 6. A Rationale for the Resistance of Dialkylbiaryl Phosphines Toward Oxidation by Molecular Oxygen. Chapter 7. Benchtop Monitoring of Reaction Progress via Visual Recognition with a Handheld UV Lamp: In Situ Sensing of Boronic Acids in the Suzuki-Miyaura Reaction. Timothy E. Barder. Ph.D. 2007-12-07T15:26:21Z 2007-12-07T15:26:21Z 2007 2007 Thesis http://hdl.handle.net/1721.1/39676 181591285 eng M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 2 v. (449 leaves ) application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Barder, Timothy E Structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines |
| title | Structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines |
| title_full | Structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines |
| title_fullStr | Structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines |
| title_full_unstemmed | Structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines |
| title_short | Structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines |
| title_sort | structural studies on biaryl phosphines and palladium complexes composed of biaryl phosphines |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/39676 |
| work_keys_str_mv | AT bardertimothye structuralstudiesonbiarylphosphinesandpalladiumcomplexescomposedofbiarylphosphines |