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43649-B3
Copper(I)-Arene Binding Studies with New Aryl-Appended Macrocyclic Ligands

Rebecca R. Conry, Colby College

        This grant is supporting efforts to follow up our previously reported results showing that the copper(I) complex of the ligand (N-ethyl-1-naphthyl)-1-aza-4,8-dithiacyclodecane exhibits copper ion binding to the pendant naphthyl group on the ligand. Thus, for that complex we determined that the naphthyl group coordinates to the copper(I) ion in an η2-fashion in both the solid state and solution. We are now focusing on the synthesis of new aryl-appended macrocylic ligands and copper(I) complexes of those ligands to more fully explore the preferences of copper(I)-arene binding.
        Our results include the synthesis of the isomeric naphthyl-appended macrocyclic ligand [(N-ethyl-2-naphthyl)-1-aza-4,8-dithiacyclodecane, 2-napL] as well as the phenyl-appended analog (PhL). The copper(I) complexes with these ligands have been prepared in small quantities and we are repeating the syntheses to fully characterize those complexes. Thus, we are working to make [2-napLCu]+ and [PhLCu]+ to probe these complexes for Cu(I)-arene interactions in solution by NMR and UV-vis spectroscopies as well as in the solid state by X-ray diffraction.
        The full-time summer 2008 research efforts of a junior undergraduate student (Thora Maltais) were supported with monies from this grant. In addition, Chantal Balesdent worked on this project part-time (for academic credit) during her senior year (this year Chantal is a first-year chemistry graduate student at the University of Oregon). Thora is now a senior and is currently looking at chemistry graduate school (instead of a medical profession) because of the experience provided by this grant. Meanwhile, she will continue her efforts on this project during this academic year. One other student (junior Kathryn Sherry) has begun learning the reactions for this project and plans to further the research project her senior year. Each of these students benefitted directly from working on the research supported by this grant. Thus, they have learned or are learning a variety of characterizational and spectroscopic techniques, such as Schlenk air-sensitive manipulations and NMR spectroscopy. The PI received partial financial compensation for the summer (less than one month's salary). However, she worked closely with the undergraduate research students on projects supported by this grant throughout the year.
        Results for the research supported under this grant were reported at the National American Chemical Society meeting in New Orleans (Spring 2008) by Chantal Balesdent. This grant supported a significant portion of her travel costs to this meeting; her poster makes up the nugget portion of this report.

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