The stepwise modifications of stoichiometric mixtures of titanium chloride (TiCl4) and titanium iso-propoxide (Ti(OPri)(4)) by 2-pyridine methanol (H-OPy) led to the isolation of a systematically varied, novel family of compounds. The 3:1 reaction mixture of Ti(OPri)(4):TiCl4 yielded [Cl(OPri)(2)Ti(mu-OPri)](2) (1). Modification of 1 with 1 and 2 equiv of H-OPy produced [Cl(OPri)(2)Ti(mu(c)-OPy)](2) (2, where mu(c) = chelating bridge) and "(OPy)(2)TiCl(OPri)" (3, not crystallographically characterized), respectively. Altering the Ti(OPri)(4) to TiCl4 stoichiometry to 1:1 led to isolation and identification of another dimeric species [Cl-2(OPri)Ti(mu-OPri)](2) (4). Upon modification with 1 equiv of H-OPy, [Cl-2(OPri)Ti(mu(c)-OPy)](2) (5) was isolated from toluene and (OPy)TiCl2(OPri)(py) (6) from py. An additional equivalent of H-OPy led to the monomeric species (OPy)(2)TiCl2 (7). Because of the low solubility and similarity in constructs of these compounds, additional analytical data, such as the beryllium dome or BeD-XRD powder analyses, were used to verify the bulk samples, which were found to be in agreement with the single crystal structures.