dc.contributor.advisor | Schley, Nathan D | |
dc.creator | Fast, Caleb Daniel | |
dc.date.accessioned | 2021-11-02T20:12:11Z | |
dc.date.available | 2021-11-02T20:12:11Z | |
dc.date.created | 2021-10 | |
dc.date.issued | 2021-10-21 | |
dc.date.submitted | October 2021 | |
dc.identifier.uri | http://hdl.handle.net/1803/16950 | |
dc.description.abstract | Catalytic C-O cleavage via ether silylation holds promise for the generation of valueadded, and biologically relevant molecules from renewable biomass-derived feedstocks. Current
catalysts for secondary C-O cleavage lack selectivity necessary for applications in the reduction
of complex substrates. Using a series of air-stable, cationic iridium bis(phosphine) catalysts has
led to the development of a tunable manifold for secondary C-O cleavage on 6-membered
carbocycles of varying complexity. We found that axial and equatorial methyl ethers show
distinct reactivity profiles. Catalyst-controlled selectivity in C-O reduction was observed.
Resting state analysis showed comparable speciation between catalysts with opposite reactivity
in the form of (PR3)2IrH4SiEt3, suggesting that selectivity is dictated by the electronic
environment of the metal center. Selectivity and mechanism of light-promoted transfer of an
iridium hydride in alkyl ether cleavage will also be discussed. | |
dc.format.mimetype | application/pdf | |
dc.language.iso | en | |
dc.subject | Iridium, catalysis, ether cleavage, hydride | |
dc.title | Designing Iridium Catalysts for Selective C-O Cleavage | |
dc.type | Thesis | |
dc.date.updated | 2021-11-02T20:12:11Z | |
dc.type.material | text | |
thesis.degree.name | PhD | |
thesis.degree.level | Doctoral | |
thesis.degree.discipline | Chemistry | |
thesis.degree.grantor | Vanderbilt University Graduate School | |
dc.creator.orcid | 0000-0001-8585-079X | |
dc.contributor.committeeChair | Schley, Nathan D | |