DIVERGENT MECHANISTIC PATHWAYS IN A METAL-CATALYZED HYDROACYLATION REACTION , AND THE ROLE PLAYED BY A HEMILABILE P-O-P LIGAND

ECU Author/Contributor (non-ECU co-authors, if there are any, appear on document)

Emily Bolger (Creator)

Institution

East Carolina University (ECU )

Web Site: http://www.ecu.edu/lib/

Abstract: The project described here involves a computational mechanistic analysis of an intermolecular hydroacylation reaction with an alkene and a beta-S-substituted aldehyde. Two products are formed in the reaction , a ketone and an ester , and the calculated reaction pathways that lead to these products begin with the same set of initial steps but diverge at a point midway through the cycle. A key component in the catalysis is the role played by the hemilabile chelating phosphine ligand. Our analysis reveals that the oxygen of the ligand remains consistently bound to the metal , and that this binding affords one of the phosphines to dissociate and thereby open up a coordination site. The divergence point allows for the coordination of two different substrates to the open coordination site. If the alkene coordinates , a ketone is ultimately produced. If a second equivalent of aldehyde coordinates , an ester is produced. The full , multi-step reaction pathways will be presented.

Additional Information

Publication

Thesis

Language: English

Date: 2017

Keywords

Chemistry, Inorganic, Computational, hemilabile

Subjects

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