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43649-B3
Copper(I)-Arene Binding Studies with New Aryl-Appended Macrocyclic Ligands
We previously reported the new ligand (N-ethyl-1-naphthyl)-1-aza-4,8-dithiacyclodecane and the copper(I) complex of this ligand. The copper(I) ion binds the naphthyl group in this complex in an η2-fashion in both the solid state and solution. This grant supports work following up this result, including the synthesis of new aryl-appended macrocylic ligands and copper(I) complexes of those ligands to learn more about the preferences of copper(I) binding to arene groups.
Our recent results include the synthesis of the closely related naphthyl-appended ligand [(N-ethyl-2-naphthyl)-1-aza-4,8-dithiacyclodecane, 2-napL] as well as the phenyl-appended analog (PhL). We have begun making and characterizing copper(I) complexes with these ligands. Some of the results of those efforts include the crystal structures of [PhLCu(PPh3)]PF6 and [2-napLCu(CH3CN)]PF6 (shown in the table of contents graphic). Unfortunately, our 400 MHz NMR spectrometer underwent fatal quenching last March (apparently the magnet reached the end of its normal life, which was over 20 years), which slowed our progress significantly. Thankfully, Colby College purchased a new 500 MHz NMR spectrometer, which is now finally operational, so that we will be making more rapid progress once again. Thus, we are working to make [2-napLCu]+ and [PhLCu]+ to probe for Cu(I)-arene interactions in those complexes.
Two undergraduate students were supported during the summer with monies from this grant. These students were: Cedric Owens the summer of 2006 and Chantal Balesdent the summer of 2007. Cedric graduated with a B.A. in chemistry at the end of May 2007 and is currently a graduate student at the University of California, Irvine. Chantal is a senior this year and is currently beginning to prepare her applications to graduate schools. Both Cedric and Chantal worked on their projects during the academic year as well. Two other students spent some or part of their senior academic year working on chemistry covered by this proposal, Colby Burns (Colby 2007, now in medical school) and Michelle Kim (Colby 2007, working in a hospital in the Boston area and assembling her medical school applications). All of these students benefited from their research experiences working on this science, including learning a variety of characterizational and spectroscopic techniques, such as Schlenk air-sensitive manipulations and NMR spectroscopy. The PI received financial compensation for both summers covered by this first, extended grant year (less than one month's salary each summer). She worked closely with the undergraduate research students on this science for a much larger period of time than she received compensation.
Results of research supported under this grant were reported at the National American Chemical Society meeting in Chicago (Spring 2007) by Cedric Owens (for which the grant supported a significant portion of his travel costs; a modified version of his poster makes up the nugget portion of this report) as well as at the Organometallics Gordon Research Conference in Newport, RI (July 2007) by the PI.
