The synthesis and characterization of new mixed-metal alkoxides of titanium with yttrium, barium, and copper, achieved via salt elimination and acid-base reactions, is described. The metathesis reactions of KTi2(OPri)(9) with anhydrous YCl3 (1:1 and 2:1) and CuCl2 (1:1) afford chloro-functionalized heterobimetallic alkoxides Cl2Y{Ti-2(OPri)(9)} (1), ClY{Ti-2(OPri)(9)}(2) (2), and ClCu{Ti-2(OPri)(9)} (3), respectively, in high yields. The barium-titanium derivatives [Ba{Ti-2(OPri)(10)}](2) (4), {Ti-2(OPri)(9)}Ba{Ti(OPri)(5)} (5), and Ba{Ti-2(OPri)(9)}(2) (6) result from the reaction between [Ba(OPri)(2)](n), and Ti(OPri)(4) in 1:2, 1:3, and 1:4 molar ratios, respectively. All the new derivatives (1-6) have been characterized by elemental analyses, variable-temperature H-1 and C-13 NMR, infrared spectroscopy, cryoscopy, and single crystal X-ray diffraction studies for 1, 3, and 5. The crystallographic study of 1 reveals a mononuclear species where the yttrium atom, coordinated by four alkoxide oxygen atoms of the {Ti-2(OPri)(9)}(-) unit and two chloride ligands, is in a pseudo-octahedral arrangement. The NMR (H-1 and C-13) and cryoscopic data for 1 indicate that the bioctahedral {Ti-2(OPri)(9)} framework, as observed in the solid state structure, is retained in solution also. The X-ray structure of copper derivative 3 exhibits a triangular heterometallic core CuTi2(mu(2)-OPri)(3)(mu(3)-OPri)(2) with chloride as a terminal ligand on copper. Each titanium bears two terminal OPri groups and displays a distorted octahedral geometry whereas copper has a pseudotrigonal bipyramidal environment. The high-temperature NMR studies for the paramagnetic 3 are in agreement with Curie law behavior; the isotropic shifts indicate that the OPri groups bound directly to the Cu-II center experience a greater paramagnetic influence in comparison to OPri groups attached to titanium only. Barium titanates reveal an interesting observation of structural and stoichiometry (Ba/Ti) change. The dimeric compound 4 (Ba/Ti, 1:2) reacts with 1 mol of Ti(OPri)(4) to offer mononuclear 5 with a Ba/Ti stoichiometry of 1:3; on further addition of 1 mol of Ti(OPri)(4), 5 is converted to 6 (Ba/Ti, 1:4). X-ray crystallography performed on 5 shows the molecular structure to be formed by the coordination of monoanionic {Ti(OPri)(5)}(-) and {Ti-2(OPri)(9)}(-) units to Ba2+ in bi- and tetradentate fashion, respectively. The coordination figure of the central atom, barium, corresponds to a trigonal prism distorted toward an octahedron. Crystal data for 1 : monoclinic space group Cc, a = 21.618(14) Angstrom, b = 9.878(5) Angstrom, c = 19.949(13) Angstrom, beta = 109.51(4)degrees, V = 4015(4) Angstrom(3), Z = 4. Crystal data for 3 : triclinic space group , a = 10.085(2) Angstrom, b = 10.210(2) Angstrom, c = 21.551(4) Angstrom, alpha = 84.40(3)degrees, beta = 84.03(3)degrees, gamma = 60.86(3)degrees, V = 1924.9(6) Angstrom(3), Z = 2. Crystal data for 5 : triclinic space group , a = 11.850(2) Angstrom, b = 13. 888(3) Angstrom, c = 18.716(4) Angstrom, alpha = 86.08(3)degrees, beta = 89.15(3)degrees, gamma = 83.36(3)degrees, V = 3052.3(11) Angstrom(3), Z = 4.