dc.creator | Chapp, Scott Matthew | |
dc.date.accessioned | 2021-06-22T16:44:08Z | |
dc.date.created | 2021-05 | |
dc.date.issued | 2021-03-09 | |
dc.date.submitted | May 2021 | |
dc.identifier.uri | http://hdl.handle.net/1803/16621 | |
dc.description.abstract | The intermolecular activation and functionalization of inert sp3 bonds using transition-metal complexes has remained a challenging area of research. Cationic dihydrido bis(phosphine) iridium complexes are found to activate ethereal sp3 C-H and C-O bonds upon dehydrogenation with tert-butylethylene (TBE). Investigation of these processes has resulted in the observation that reversible intramolecular phosphine cyclometalation can precede intermolecular C-O bond cleavage of methy tert-butyl ether (MTBE) and is a competing kinetic pathway in the first example of alkane dehydrogenation. Related studies using a cationic PNP pincer-supported iridium complex have shown the facile formation of an alkoxycarbene derived from α,α-dehydrogenation of cyclopentyl methyl ether (CPME) and demonstrate its reactivity in atom- and group-transfer reactions. In this system, metoxytrimethyl silane does not undergo α,α-dehydrogenation to give the corresponding siloxymethylidene, instead reacting by Si-CH3 oxidative addition. The generality of this transformation across a family of organosilanes has allowed an in-depth analysis of the kinetic and thermodynamic effects at play in sp3 Si-C oxidative addition and reductive elimination. | |
dc.format.mimetype | application/pdf | |
dc.language.iso | en | |
dc.subject | alkoxycarbene | |
dc.title | Activation of Inert sp3 C-H, C-O and C-Si Bonds at Cationic Iridium Complexes | |
dc.type | Thesis | |
dc.date.updated | 2021-06-22T16:44:08Z | |
dc.type.material | text | |
thesis.degree.name | PhD | |
thesis.degree.level | Doctoral | |
thesis.degree.discipline | Chemistry | |
thesis.degree.grantor | Vanderbilt University Graduate School | |
local.embargo.terms | 2023-05-01 | |
local.embargo.lift | 2023-05-01 | |
dc.creator.orcid | 0000-0001-6293-7948 | |
dc.contributor.committeeChair | Schley, Nathan D | |