dc.contributor.advisor | Alexander Radosevich. | en_US |
dc.contributor.author | Lin, Yi-Chun, Ph. D. Massachusetts Institute of Technology | en_US |
dc.contributor.other | Massachusetts Institute of Technology. Department of Chemistry. | en_US |
dc.date.accessioned | 2018-03-02T22:21:33Z | |
dc.date.available | 2018-03-02T22:21:33Z | |
dc.date.copyright | 2017 | en_US |
dc.date.issued | 2017 | en_US |
dc.identifier.uri | http://hdl.handle.net/1721.1/113980 | |
dc.description | Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2017. | en_US |
dc.description | Cataloged from PDF version of thesis. Vita. | en_US |
dc.description | Includes bibliographical references. | en_US |
dc.description.abstract | Molecular 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.statementofresponsibility | by Yi-Chun Lin. | en_US |
dc.format.extent | 379 pages | en_US |
dc.language.iso | eng | en_US |
dc.publisher | Massachusetts Institute of Technology | en_US |
dc.rights | MIT 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.uri | http://dspace.mit.edu/handle/1721.1/7582 | en_US |
dc.subject | Chemistry. | en_US |
dc.title | Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds | en_US |
dc.type | Thesis | en_US |
dc.description.degree | Ph. D. | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | |
dc.identifier.oclc | 1023628472 | en_US |