Elucidation of Metal-Sugar Complexes: When Tungstate Combines with D-Mannose

The control of metal-sugar complexes speciation in solution is crucial in an energy transition context. Herein, t h e formation of tungstate-mannose complexes is unraveled in aqueous solution using a multitechnique experimental and theoretical approach. 13C nuclear magnetic resonance (NMR), as well as 13C-1H and 1H-1H correlation spectra, analyzed in the light of coordination-induced shift method and conformation analysis, were employed to characterize the structure of the sugar involved in the complexes. X-ray absorption near edge structure spectros-copy was performed to provide relevant information about t h e metal electronic and coordination environment. The calculation of 13C NMR chemical shifts for a series of tungstate-mannose complexes using density functional theory (DFT) is a key to ident i f y the appropriate structure among several candidates. Furthermore, a parametric study based on several relevant parameters, namely, pH and tungstate concentration, was carried out to look over the change of the nature and concentrations of the complexes. Two series of complexes were detected, in which the metallic core is either in a ditungstate or a monotungstate form. With respect to previous proposals, we identify two new species. Dinuclear complexes involve both alpha- and beta-furanose forms chelating the metallic center in a tetradentate fashion. A hydrate form chelating a ditungstate core is also revealed . One monotungstate complex appears at high pH, in which a tetrahedral tungstate center is bound to alpha-mannofuranose through a monodentate site at the second deprotonated hydroxyl group. This unequalled level of knowledge opens the door to structure-react i v i t y relationships.

Automated summary

The formation of tungstate-mannose complexes in aqueous solution was characterized using a combination of experimental and theoretical techniques. The structures of the complexes were determined using NMR and X-ray absorption spectroscopy. The study identified new complexes and provided insights into the structure-reactivity relationships of these metal-sugar complexes.