Gallium and indium complexes of N,N’-bis(2-hydroxybenzyl)-N,N’-bis(2-methylpyridyl)ethylenediami (H(2)bbpen), N,N’-bis(S-bromo-2-hydroxybenzyl)-N,N-bis(2-methylpyridyl)ethylenediamine (H(2)Bbbpen), and N,N’-bis(5-chloro-2-hydroxybenzyl)-N,N-bis (2-methylpyridyl)ethylenediamine (H(2)Clbbpen) were prepared and characterized by spectroscopic techniques and crystallographic analyses. H(2)bbpen, H(2)Brbbpen, and H(2)Clbbpen were prepared in excellent yield by the reactions of 2-picolyl chloride with N,N’-bis(2-hydroxybenzyl)ethylenediamine (H-2- bben),N,N’-bis(S-bromo-2-hydroxybenzyl)ethylenediamine (HzBrbben), and N,N’-bis(S-chloro-2-hydroxybenzyl)ethylenediamine (H(2)Clbben), respectively. Characterization of H(2)bbpen and its substituted analogs showed these compounds to be symmetrical about the ethylene moiety of the ethylenediamine backbone. This symmetry is maintained in the metal complexes of these compounds. There are six potential sites for coordination to a metal ion : two amine nitrogens, two phenolate oxygens, and two pyridyl nitrogens. A series of monocationic metal complexes were obtained from the reactions of Ga3+ and In3+ with H(2)bbpen, H(2)Brbbpen, and H(2)Clbbpen in the presence of 2 equiv of base (acetate). Crystals of [Ga(Clbbpen)]ClO4 are triclinic, of space group P ($) over bar 1, with 11.1563(6) Angstrom, b = 14.1365(6) Angstrom, c = 9.9296(7) Angstrom, alpha = 98.395(4)degrees, beta = 107.094(5)degrees, gamma = 70.751(4)degrees, and Z = 2, and those of [In(Clbbpen)]ClO4 are monoclinic, of space group P2(1)/c, with a = 9.693(1) Angstrom, b = 21.821(2) Angstrom, c = 14.428(1) Angstrom, beta = 109.413(7)degrees, and Z = 4. The structures were solved by heavy atom methods and were refined by full-matrix least-squares procedures to R = 0.035 and 0.030 for 5777 and 6002 reflections with I greater than or equal to 3 because sigma(I), respectively. Both Ga3+ and In3+ were coordinated in a distorted octahedral geometry by an N2N’O-2(2) donor set. Greater distortion was observed in the octahedral geometry of the [In(Clbbpen)]ClO4 complex versus the [Ga(CIbbpen)]ClO4 complex. H-1 NMR spectral data of the metal complexes showed rigid solution structures for all the Ga and In complexes; no evidence of fluxional behavior was observed at solution temperatures as high as 120 degrees C.