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dc.contributor.advisorAlexander Radosevich.en_US
dc.contributor.authorLin, Yi-Chun, Ph. D. Massachusetts Institute of Technologyen_US
dc.contributor.otherMassachusetts Institute of Technology. Department of Chemistry.en_US
dc.date.accessioned2018-03-02T22:21:33Z
dc.date.available2018-03-02T22:21:33Z
dc.date.copyright2017en_US
dc.date.issued2017en_US
dc.identifier.urihttp://hdl.handle.net/1721.1/113980
dc.descriptionThesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2017.en_US
dc.descriptionCataloged from PDF version of thesis. Vita.en_US
dc.descriptionIncludes bibliographical references.en_US
dc.description.abstractMolecular distortion has a profound impact on the electronic structure and reactivity of molecules. This dissertation describes studies on E-H bond activation and catalytic reactivity of [sigma]³- and [sigma]⁴ -phosphorus compounds with distorted nontrigonal structures. Specifically, a rare example of N-H oxidative addition to a planar, C2v-symmetric P(III) center is described in Chapter 2. The kinetics and computational studies implicate a noncanonical, phosphorus-based electrophilic pathway for this transformation. As detailed in Chapter 3, a Cs-symmetric phosphorous triamide and its P-N cooperative reactivity are presented. B-H activation and catalytic imine hydroboration are achieved via the combination of the electrophilic phosphorus center and the basic anilide ligand moiety of this Cs-symmetric phosphorus compound. Finally, Chapter 4 extends the study of distorted phosphorus compounds to [sigma]⁴ -phosphorus molecules. Iminophosphoranes bearing constrained ligand platforms are synthesized and their distortion-induced B-H, B-O and Si-H bond activation reactivity are presented. This research provides insight into the influence of molecular symmetry on the reactivity of [sigma]³- and [sigma]⁴-phosphorus compounds and represents an initial step toward the discovery of new chemistry in other distorted phosphorus molecules.en_US
dc.description.statementofresponsibilityby Yi-Chun Lin.en_US
dc.format.extent379 pagesen_US
dc.language.isoengen_US
dc.publisherMassachusetts Institute of Technologyen_US
dc.rightsMIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.en_US
dc.rights.urihttp://dspace.mit.edu/handle/1721.1/7582en_US
dc.subjectChemistry.en_US
dc.titleBond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compoundsen_US
dc.typeThesisen_US
dc.description.degreePh. D.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistry.en_US
dc.identifier.oclc1023628472en_US


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