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The structure of d xylo 5 hexulosonic acid and its gadolinium iii complexes in aqueous medium as studied by nmr


, : The structure of d xylo 5 hexulosonic acid and its gadolinium iii complexes in aqueous medium as studied by nmr. Journal of the Chemical Society Dalton Transactions (9): 2707-2712

The solid-state 13C n.m.r. spectrum of calcium D-xylo-5-hexulosonate, which exists exclusively in the .beta.-furanose form, resembles that of the minor furanose form in solution. A 1H two-dimensional nuclear Overhauser enhancement spectrum (NOESY), however, unambiguously shows that the latter component is the .alpha.-furanose form. Thus caution is required in comparing liquid- and solid-state n.m.r. spectra. Longitudinal relaxation-rate measurements show that GdIII binds preferentially to the keto tautomer, in a bidentate fashion via a carboxylate oxygen and O(2). The first co-ordination sphere of GDIII in the predominant complex is completed by furanose ligands bound in a bidentate manner via the two carboxylate oxygens.

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