In methanol, the reaction of Ti(O i Pr) 4 , N-(2-hydroxyphenyl)salicylideneimine (H 2 Sap) and 8-hydroxyquinoline (HQ) in stoichiometric ratio 1:1:x yielded Ti(Sap) 2 precipitate as initial product even when x was as high as 10. However, when the reaction mixture with x=2 was left standing for 12h or more, a small amount of red crystalline Ti(Sap)Q(OMe) was isolated. Addition of wet acetonitrile to the reaction mixture with x=10, small amount of another red crystalline [Ti(Sap)Q] 2 (μ-O) was obtained after standing for 2 days. The reaction between TiQ 2 (O i Pr) 2 and H 2 Sap in methanol with stoichiometric ratio of y:1 also yielded Ti(Sap) 2 as initial product even for y as large as 10. 1 H NMR investigation of the reaction of TiQ 2 (OMe) 2 with H 2 Sap revealed that Ti(Sap)Q(OMe) was not detected initially. These experimental results can be explained based on a mechanism that includes: (i) rapid reaction of H 2 Sap with Ti(IV) centers to form Ti(Sap) 2 ; (ii) equilibrium between TiQ 2 (OMe) 2 and Ti(Sap)Q(OMe); (iii) equilibrium between Ti(Sap)Q(OR) and Ti(Sap) 2 ; and (iv) limited solubilities of Ti(Sap)Q(OR) and Ti(Sap) 2 . The equilibrium constants and solubilities in the mechanism were determined by the 1 H NMR spectral method. The structures of Ti(Sap)Q(OMe) and [Ti(Sap)Q] 2 (μ-O), consisting octahedrally coordinated Ti(IV), were determined by X-ray diffraction method.