Abstract
Abstract C-13 NMR longitudinal relaxation times have been measured for lariat ether complexes in which a negative charge is present in the ligand but the system is diamagnetic. A -CH2COO− group connected to the nitrogen of aza-15-crown-5 results in drastically increased T1's in the presence of Li+ compared to the values for the free carboxylic acid and for the acid in the presence of LiClO4. Longer relaxation times upon complexation show the ‘cryptand-like’ behavior of the complexes, resulting from overall molecular reorientation rates due to compression. These conclusions are supported by molecular mechanics calculations described herein.
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