Cation co-ordination has been studied in aqueous cation-borate-D-glucarate systems using "B n.m.r. spectroscopy. The univalent cations K1, Nal, and Agl do not show preferential co-ordination by the borate esters of D-glucarate. The divalent cations Mg", Call, Coil, Nil1, Sr", C d Y and Ball are co-ordinated by the borate diesters. The cations that ionize the a-hydroxyl functions of Dglucarate, Cull, Zn", Prlll, and Pb", and/or compete with borate for the diol functions, and Fell1, are more strongly co-ordinated by free o-glucarate than by its borate diester. The different behaviour of the cations is discussed in terms of differences in charge/radius density and polarizing ability. In the CaI I-oxyacid anion-o-glucarate system, Call ion-selective electrode measurements and CaI I sequestering capacity determinations have been performed. Apart from borate, synergic Call co-ordination is observed at high p H for the oxyacid anion esters of D-glucarate of antimonite, stannate, aluminate, and germanate.Aqueous alkaline solutions of borate and polyhydroxycarboxylates possess good cation sequestering abilities and are applied in the galvanic, glass, and cement industries, and in pharmaceutical^.^ In addition, these systems have potential as triphosphate substitutes in detergent^.^,^ We have determined the stability and structure of borate mono-and di-esters of a series of polyhydroxycarboxylates (Figure 1) using multinuclear n.m.r. ~p e c t r o s c o p y . ~* ~The synergic Ca" co-ordination in these systems finds its origin in the high Ca" co-ordinating strength of the borate diesters of the polyhydroxycarboxylates.2-8 This effect is most pronounced for D-glucarate (Figure 2) as the polyhydroxy~arboxylate.~~~~~ Formation of the threo-3,4borate diesters of D-glucarate results in the creation of new multidentate Ca" co-ordinating sites.' Each of these sites is composed of two carboxylate oxygens, two borate ester ring oxygens, and, depending on the configuration, up to two hydroxyl oxygens (Figure 3).2*8 Borate (B"') is not unique in forming oxyacid anion esters (or complexes) with diol functions. Other oxyacid anions (X -) such as aluminate (Al"'), silicate (Si"), germanate (Gel'), arsenite (As"'), selenite (SeIV), stannate (Sn"), antimonate (Sb'), tellurate (Te"), and periodiate (Iv") are also capable of doing