Author (Your Name)

Paul J. Lee, Colby College

Date of Award


Document Type

Honors Thesis (Open Access)


Colby College. Chemistry Dept.


Rebecca R. Conry


Two macrocyclic ligands with a pendant phenyl group -N-[2-(l-phenyl)ethyl]-1-aza-4,8di thiacyclodecane (L1) and N-[2-0-phenyl)propyl]-1-aza-4,8-dithiacyclodecane, (L2) has been synthesized and characterized. The copper(I)-triphenylphosphine complex [LICu(PPhJ)]OTf , (2) was synthesized from L1 1/2(C6H6)[CuOTf]2, and PPh3. The complexes [LICu]OTf 1 and [L2Cu]OTf 3 were also synthesized and characterized using DC and IH NMR, UV-vis and lR spectroscopy, and ESI-MS. In CD2Cl2, 1 was found to have a fluxional behavior with the barrier ΔG to the process estimated at 9-11 kcal/mol. Variable temp. NMR spectroscopy of 1 gave compelling evidence that the phenylappended group is bound in an intramolecullar η2-fashion with the copper center. At room temperature, 1 and 3 were found to be in a fluxional process of the bound and unbound arene system. In CD2CI2 the barrier to the fluxional process for 2 was found to be much less than 1; ΔG = 2-8 keal/mol. The location of binding on the aryl linker arm for 1 and 3 is hypothesized to be at the π-system adjacent to the linker arm. (DFT) pBP/DN• and RHF -6-31 g* molecular orbital calculations have been performed to better understand the complexes 1 and 3.


Cooperative binding, Ligand binding, Aromatic compounds, Copper, arene interactions, NS2-macrocyclic ligand, pendant aryl arms

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