Sugar phosphates provide metal-binding sites both at their sugar core and at their phosphate group(s). Mixed sugar-core-phosphate chelation has been considered as a typical bonding mode within the physiological pH range for the central metabolite D-fructose 1,6-bisphosphate. The (ReO)-O-V(tmen) metal fragment was used to enrich this coordination type. The formation of the ReO(tmen)(Fruf2,3H(-2)1,6-P2H2-kappa O-3(2,3,P1))](-) monoanion was determined by NMR spectroscopy and mass spectrometry. The model compound rac-glycerol 1-phosphate yielded similar results in terms of NMR spectroscopy. Crystal-structure analyses of ReO(tmen)(rac-Glyc2,3H(-2)1PH-kappa O-3(2,3,P))]center dot 2H(2)O and ReO(phen)(rac-Glyc2,3H(-2)1PH-kappa O-3(2,3,P))]center dot MeOH confirmed the coordination pattern.