The coordination behavior of a series of group 4 metal alkoxides [M(OR)(4)] modified by a set of novel substituted hydroxybenzyl ethylene diamine (H-4-ED-L-4) ligands {[tetra(3,5-di-t-butyl-2-hydroxybenzyl)-N,N'-ethylenediamine] termed H-4-ED-DBP4 (1), [tetra(3,5-di-t-amyl-2-hydroxybenzyl)-N,N'-ethylenediamine] termed H-4-ED-DAP(4) (1a), and [tetra(3',5-dichloro-2-hydroxybenzyl)-N,N'-ethylenediamine] termed H-4-ED-DCP4 (2)} was elucidated. The reaction of 1 or 1a with the M(OR)(4) precursor led to the isolation of the structural similar species M(ED-L-4) where L = DBP, M=Ti (3), Zr (4), Hf (5); L = DAP, M = Zr (4a), Hf (5a). In contrast, the reaction of 2 with the M(OR)(4) precursors yielded Ti(ED-DCP4) (6). (py)(2)Zr(ED-DCP4) (7), and (HOBut)Hf(ED-DCP4) (8) where py = pyridine and HOBut = HOC(CH3)(3). For 3-6, the cations of the monomeric species were completely encapsulated by all available heteroatoms (four O and two N) of the ED-L-4 ligands, yielding an octahedral geometry for each metal center. For 7 and 8, an identical binding by the ED-DCP4 ligand was observed with the additional coordination of Lewis basic adducts, forming 8- and 7-coordinated metal centers, respectively. Switching to +2 cations led to the isolation of [(THF)Ca](2)(ED-DBP4) (9a) where THF=tetrahydrofuran, {[(py)Ca](4)(ED-(mu-DBP-eta(6))(4))(2)}(n) (9b), and [(py)Zn](ED-DBP4)[Zn(py)(2)] (10) center dot 5py and [(py)Sn](2)(ED-DBP4) (11). The structures of these species were significantly different in arrangement compared to the Group 4 derivatives. Further attempts to produce a mixed +4/+2 cationic species yielded [(py)(ONep)(2)Ti(ED-DBP4)Zn(py)] (12). Reacting the single-source precursor CO[mu-OC6H4(CHMe2)(2)center dot 2)(2)Li-(py)(2)](2) with 1, led to the isolation of (py)Li[Eb-DBP3(H-DBP)]Co (13), with one of the phenol protons remaining unreacted. The synthesis and characterization of these compounds are presented in detail.