Isomerization is a synthetically useful technique to form the more stable internal alkene from terminal alkene feedstock. Unfortunately, these transformations form a variety of isomers without catalyst control. Z alkenes are thermodynamically challenging to form compared to their E counterparts but are useful in pharmaceutical, fragrance, and flavor industries, making them sought-after products. Therefore, catalysts targeting specific regio- and stereoisomers, particularly Z alkenes, will benefit many fields. This work analyzes several Mo(0) complexes as Z-2-alkene selective isomerization catalysts. Particular focus has been given to cis-Mo(CO)4(PCy3)(piperidine) due to easy purification and characterization. Substantial improvement to reported Z selectivities have been obtained with this complex, though disadvantages exist. To have a clearer understanding of the mechanism and source of Z selectivity, DFT analysis was completed, and a mechanism proposed. A rare rotation of hydride and carbonyl ligands was found, only reported in one prior Mo complex, that facilitates the isomerization. Key characteristics were discovered that will be applied to develop future iterations with the goal of reducing, or removing, the disadvantages of this system. / Chemistry
| Identifer | oai:union.ndltd.org:TEMPLE/oai:scholarshare.temple.edu:20.500.12613/8687 |
| Date | January 2022 |
| Creators | Jenny, Sarah, 0000-0001-5455-4090 |
| Contributors | Dobereiner, Graham, Valentine, Ann M., Zdilla, Michael J., 1978-, Nova, Ainara |
| Publisher | Temple University. Libraries |
| Source Sets | Temple University |
| Language | English |
| Detected Language | English |
| Type | Thesis/Dissertation, Text |
| Format | 458 pages |
| Rights | IN COPYRIGHT- This Rights Statement can be used for an Item that is in copyright. Using this statement implies that the organization making this Item available has determined that the Item is in copyright and either is the rights-holder, has obtained permission from the rights-holder(s) to make their Work(s) available, or makes the Item available under an exception or limitation to copyright (including Fair Use) that entitles it to make the Item available., http://rightsstatements.org/vocab/InC/1.0/ |
| Relation | http://dx.doi.org/10.34944/dspace/8651, Theses and Dissertations |
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