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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

DEVELOPMENT OF Mo(0) COMPLEXES FOR THE SELECTIVE ISOMERIZATION OF Z-2-ALKENES FROM TERMINAL ALKENES

Jenny, Sarah, 0000-0001-5455-4090 January 2022 (has links)
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

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