X-ray structural characterization of a new isomer of ReO(TMECH3) revealed that it is anti-ReO(DL-TMECH3) (Ij. (DL-TNLECH6 is meso-tetramethyl-ethylene-dicysteine prepared from racemic penicillamine (penH(4)), the subscript on H indicating the number of dissociable protons; anti denotes the geometric isomer having both carboxyl groups anti to the oxo ligand.) In I, one carboxyl is deprotonated and coordinated trans to the oxo ligand, and the other is protonated and dangling. The H-1 NMR spectrum (assigned by 2D methods) of 1 at pH 4 in aqueous solution revealed that the structure of 1 is the same as in the solid state except for deprotonation of the dangling carboxyl group, affording the monoanion. All chelate ring protons and methyl groups are inequivalent and give sharp signals. As the pH was raised above 7, the ID H-1 NMR signals of the monoanion broadened. Broadening was severe for the methyl and ethylene signals of the tridentate half of the monoanion, and these signals were replaced by new signals for the dianion. The changes suggested a rate process that was intermediate on the NMR time scale, such as CO2- ligation/deligation. With increasing pH the dianion signals sharpened up to pH similar to 8 and then broadened up to pH approximate to 10. Finally, the spectrum at pH 10.8 showed only half the number of signals. Each signal was at the midpoint shift between two corresponding signals observed at lower pH, indicating a time averaging between the halves of the DL-TMEC ligand, but no change in protonation state. Two Re=O stretching bands (923 and 933 cm(-1)) with a constant intensity ratio of similar to1 were observed for the dianion. These results can be explained if the dianion exists detectably only as a NH-deprotonated/carboxyl-deligated form having two conformers. The conformers differ in the N lone pair (NLp) orientation (either endo or exo with respect to the oxo ligand) and thus have slightly different Re=O stretching frequencies. Although they can be detected by resonance Raman spectroscopy, the conformers are indistinguishable by NMR spectroscopy because NLp inversion land hence conformer interconversion) is very fast. Interchange of the NH and NLp sites affects the NMR spectra. At pH 8.3 the signals of the dianion are sharpest because interchange is slowest. Below and above pH 8.3, the signals are broader because acid and base catalysis, respectively, increase the rate of interchange between the NH and NLp sites.