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The Reactivity of Eta-2-Aminoarenes Coordinated to Tungsten Via Acid Trapping

Pienkos, Jared
Thesis/Dissertation; Online
Pienkos, Jared
Harman, Walter
PIENKOS, JARED A. The Reactivity of η2-Aminoarenes Coordinated to Tungsten via Acid Trapping (Under the direction of Professor W. Dean Harman) The Harman lab exploits π-basic metal fragments to functionalize arenes. Coordination of an aromatic molecule to a π-basic metal fragment usually occurs in an η2-fashion. In the process of complexation, the arenes are dearomatized, and the resulting ligands are able to undergo synthetic transformations that are inaccessible to the unbound, organic analogs.(1) Currently, the [TpW(NO)(PMe3)] metal fragment is used as a dearomatization reagent because of its low cost, scalability, and accessibility to a TpW(NO)(PMe3)(η2-benzene) complex. The η2-coordinated benzene can be substituted with a variety of aromatic ligands.(2) For example, an aromatic ring with an amine moiety can be exchanged with tungsten-bound benzene and protonated in situ, forming its conjugate acid. This product, although cationic, is able to undergo a second electrophilic addition. Modifications of these bound arenes result in the formation of novel organometallic derivatives. Friedel-Crafts, (3) hydroamination, and cyclopropanation (4) reactions have been performed on these coordinated η2-aminoarenes. In some cases, after synthetic modifications, the functionalized ligand can be removed from the metal fragment. This strategy has been used to generate cyclohexenone, amidine, and hexahydroindole derivatives. References: (1) Keane, J. M.; Harman, W. D. Organometallics 2005, 24, 1786. (2) Welch, K. D.; Harrison, D. P.; Lis, E. C.; Liu, W.; Salomon, R. J.; Harman, W. D.; Myers, W. H. Organometallics 2007, 26, 2791. (3) Pienkos, J. A.; Zottig, V. E.; Iovan, D. A.; Li, M.; Harrison, D. P.; Sabat, M.; Salomon, R. J.; Strausberg, L.; Teran, V. A.; Myers, W. H.; Harman, W. D. Organometallics 2013, 32, 691. (4) Pienkos, J. A.; Knisely, A. T.; Liebov, B. K.; Teran, V.; Zottig, V. E.; Sabat, M.; Myers, W. H.; Harman, W. D. Organometallics 2013, 33, 267.
University of Virginia, Department of Chemistry, PHD (Doctor of Philosophy), 2014
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PHD (Doctor of Philosophy)
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