The first pseudooctahedral tris(binaphtholates) of first-row transition elements, Na-3[Fe(S-binaphtholate)(3)]. 3Et(2)O H2O (1), Li-3[Fe(R-binaphtholate)(3)]. 6THF (2), and Li-3[Cr(R-binaphtbolate)3]. 6THF (3), are heterobimetallic complexes incorporating alkali metal ions. 1 crystallizes in the monoclinic spacegroup P2(1) with a = 11.3256(10) A, b = 20.735(3) Angstrom, c = 13.5741(15) Angstrom, beta = 91.086(8)degrees, and Z = 2. 2 and 3 are isomorphous, crystallizing in the hexagonal space group P6(3)22 with a = 14.897(15) Angstrom, b = 19.284(19) Angstrom, and Z = 2 (2) and a = 14.850(4) Angstrom, b = 19.052(7) Angstrom, and Z = 2 (3). The CD and absorption spectra of the Fe(III) and Cr(III) compounds are discussed and compared with those reported for [Fe(enterobactin)](3-) and model compounds and for [Cr(entereobactin)](3-), respectively.