trans-Cyclooctanediyl-bridged [OSSO]-type ligand 4 reacts with TiCl4(thf)(2) in toluene to produce the corresponding titanium(IV) dichloro complexes as an inseparable mixture of cis-alpha isomer 6a and cis-beta isomer 6b in a ratio of 2:1, whereas treatment of dilithio salt of 4 with TiCl3(thf)(3) in Et2O afforded chloride-bridged dimeric titanium(III) complex 8, which indicated the antiferromagnetic character in a nonpolar solvent solution. Di(isopropoxy) titanium(IV) complex 10 having a C-2-symmetric cis-alpha configuration was synthesized by the reaction of 4 with Ti((OPr)-Pr-i)(4) in toluene as yellow crystals. Moreover, the reaction of 4 with Ti(NEt2)(4) in toluene resulted in the unexpected formation of [OSSO]-type bis(phenolato)-bridged dinuclear