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dc.contributor.advisorStephen L. Buchwald.en_US
dc.contributor.authorBarder, Timothy Een_US
dc.contributor.otherMassachusetts Institute of Technology. Dept. of Chemistry.en_US
dc.date.accessioned2007-12-07T15:26:21Z
dc.date.available2007-12-07T15:26:21Z
dc.date.copyright2007en_US
dc.date.issued2007en_US
dc.identifier.urihttp://hdl.handle.net/1721.1/39676
dc.descriptionThesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007.en_US
dc.descriptionThis electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.en_US
dc.descriptionVita.en_US
dc.descriptionIncludes bibliographical references.en_US
dc.description.abstractPd-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.en_US
dc.description.abstract(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.en_US
dc.description.statementofresponsibilityTimothy E. Barder.en_US
dc.format.extent2 v. (449 leaves )en_US
dc.language.isoengen_US
dc.publisherMassachusetts Institute of Technologyen_US
dc.rightsM.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.en_US
dc.rights.urihttp://dspace.mit.edu/handle/1721.1/7582
dc.subjectChemistry.en_US
dc.titleStructural studies on biaryl phosphines and palladium complexes composed of biaryl phosphinesen_US
dc.typeThesisen_US
dc.description.degreePh.D.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistry
dc.identifier.oclc181591285en_US


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