Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2017.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2018
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| Online Access: | http://hdl.handle.net/1721.1/113980 |
| _version_ | 1826209568287358976 |
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| author | Lin, Yi-Chun, Ph. D. Massachusetts Institute of Technology |
| author2 | Alexander Radosevich. |
| author_facet | Alexander Radosevich. Lin, Yi-Chun, Ph. D. Massachusetts Institute of Technology |
| author_sort | Lin, Yi-Chun, Ph. D. Massachusetts Institute of Technology |
| collection | MIT |
| description | Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2017. |
| first_indexed | 2024-09-23T14:24:32Z |
| format | Thesis |
| id | mit-1721.1/113980 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T14:24:32Z |
| publishDate | 2018 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/1139802019-04-11T04:26:25Z Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds Lin, Yi-Chun, Ph. D. Massachusetts Institute of Technology Alexander Radosevich. Massachusetts Institute of Technology. Department of Chemistry. Massachusetts Institute of Technology. Department of Chemistry. Chemistry. Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2017. Cataloged from PDF version of thesis. Vita. Includes bibliographical references. 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. by Yi-Chun Lin. Ph. D. 2018-03-02T22:21:33Z 2018-03-02T22:21:33Z 2017 2017 Thesis http://hdl.handle.net/1721.1/113980 1023628472 eng 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. http://dspace.mit.edu/handle/1721.1/7582 379 pages application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Lin, Yi-Chun, Ph. D. Massachusetts Institute of Technology Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds |
| title | Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds |
| title_full | Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds |
| title_fullStr | Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds |
| title_full_unstemmed | Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds |
| title_short | Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds |
| title_sort | bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/113980 |
| work_keys_str_mv | AT linyichunphdmassachusettsinstituteoftechnology bondactivationandcatalysisbynontrigonaltricoordinateandtetracoordinatephosphoruscompounds |