Bond activation and catalysis by nontrigonal tricoordinate and tetracoordinate phosphorus compounds

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.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2017

Author dc:creator

• Lin, Yi-Chun, Ph. D. Massachusetts Institute of Technology

Advisor dc:contributor.advisor

• Alexander Radosevich.

• Chemistry.

Statement 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.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/113980

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/113980