The diacetone glucose (DAGH, 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose) monoanion DAG binds as a terminal alkoxo ligand to a variety of transition metals. When it is used in excess, with respect to the oxidation state of the metal, homoleptic anionic complexes [M'(DAG)(6)](3-) are formed. Such complexes contain oxygen-rich cavities between pairs of DAG ligands appropriate for binding alkali metal cations. The anionic complexes have been obtained by using [Li(DAG)I, 1, and [Na(DAG)I, 2, whose syntheses and characterization are reported here. The reaction of 1 and 2 with [V(DAG)(3)] gave [V(DAG)(6)Li-3], 3, and [V(DAG)(6)Na-3], 4, respectively. An alternative synthesis of 3 and 4 involves the metathesis reaction of 1 land 2 with [VCl3(thf)(3)]. This strategy also led to the synthesis of [Cr(DAG)(6)Li-3], 5, and [Ti(DAG)(6)Li-3], 6. Three pairs of DAG shape a cavity appropriate for three lithium cations in the case of complexes 3, 5, and 6; a cavity is formed for three sodium cations in the case of 4, where the alkali cation is in a tetrahedral O-4 environment. In the anionic manganese derivative [Mn(Cl)(DAG)(4)](3-), the four DAG units arrange in such a way as to bind four Li cations, which form a cationic cage [Mn(Cl)(DAG)(4)Li-4](+), and Cl- is bound inside as [Mn(Cl)(DAG)(4)Li-4(mu(4)-Cl)], 7. Crystallographic details : 4, prism, P2(1), a 14.735(10) Angstrom, b = 15.033(9) Angstrom, c = 21.021(10) Angstrom, beta = 107.34(2)degrees, V = 4445(5) Angstrom(3), Z = 2, and R = 7.60; 5, prismatic, C2, a = 22.671(9) Angstrom, b = 18.785(5) Angstrom, c = 13.886(4) Angstrom, beta = 126.39(2)degrees, V = 4761(3) Angstrom(3), Z = 2, and R = 7.32; 6, prismatic, P2(1), a 13.888(5) Angstrom, b = 18.750(5) Angstrom, c = 17.933(5) Angstrom, beta = 91.84(2)degrees, V = 4667(2) Angstrom(3), Z = 2, and R = 8.75; 7, prismatic, P2(1), a 13.306(7) Angstrom, b = 21.311(11) Angstrom, c =13.376(6) Angstrom, beta = 95.01(2)degrees, V = 3779(3) Angstrom(3), Z = 2, and R = 9.33.