The reaction of [Ti(mu-ONep)(ONep)(3)](2) (ONep = OCH2C(CH3)(3)) with a series of heterocyclic methanol derivatives [tetrahydrofurfuryl alcohol (H-OTHF), thiophene methanol (H-OTPM), or 2-pyridylcarbinol (H-OPy)collectively termed H-OR*], led to the isolation of a novel family of OR*-substituted titanium alkoxide precursors. Independent of the initial stoichiometry for the H-OTHF reaction, a monosubstituted, dinuclear species was isolated as [(ONep)(3)Ti(mu(c)-OTHF)](2) (1). For 1, each Ti was octahedrally (Oh) bound by three terminal ONep ligands, one bidentate bridging OTHF ligand (mu(c)-OTHF), and an oxygen from the other mu(c)-OTHF ligand. For the OTPM derivatives, the product was identified as [(ONep)(3)Ti(mu-OTPM)](2) (2). For this ligand, the soft S atom does not bind to the Ti but the O atom does act as a bridge between the two trigonal bipyramidal bound Ti metal centers. The OPy system yielded (OPy)(2)Ti(OR)(2) independent of the OR and the stoichiometry used [OR = ONep (3), OCHMe2 (4), OCMe3 (5)]. For 3-5, the two OPy ligands chelate to the Oh-bound Ti metal center with two terminal OR ligands. Compounds 1-5 were fully characterized using a variety of analytical techniques. An initial investigation of the proposed chemical stability of the '(OPy)(2)Ti' moiety of 3-5 to alcoholysis exchange pathways involving (i) alkyl alcohols, (ii) aryl alcohols, (iii) substituted phenols, (iv) H-OR* derivatives, and (v) silanols proved successful through the isolation of a novel family of structurally characterized (OPy)(2)Ti(OR')(2) (7-24) compounds.