Efforts Toward the Site-Selective Dehydrogenation of Saturated Fatty Acids

Studies toward the selective functionalization of saturated fatty acids using iridium carboxylate complexes are described. A variety of iridium complexes were developed bearing a coordinated carboxylate ligand. These complexes were submitted to known dehydrogenation conditions; however, dehydrogenation products were not observed. The bidentate binding of the carboxylate was thought to be responsible for the lack of reactivity observed in these complexes. The carboxylate ligands were therefore derivatized in an effort to favor monodentate coordination. Acylphosphine ligands, which are readily synthesized from fatty acids, were of particular interest due to the long phosphorus carbonyl bond distance relative to the oxygen carbonyl bond distance in carboxylates. Initial studies using acylphosphines resulted in the synthesis of a novel anionic complex. The structural characterization and reactivity of this complex is discussed. Continued work with acylphosphines led to the discovery of a unique site-selective dehydrogenation reaction. A plausible mechanism for this transformation is proposed based on the isolation of observed intermediates and computational studies.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

The Ohio State University

Year dc:date

2013

Author dc:creator

• Whittemore, Sean M.

Contributors dc:contributor

• Stambuli, James

• Chemistry

Statement dc:rights

• unrestricted
• This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.

Language dc:language

English

Repository record dc:identifier

http://rave.ohiolink.edu/etdc/view?acc_num=osu1366198700

OAI identifier oai:identifier

oai:etd.ohiolink.edu:osu1366198700