A variety of aryloxy compounds and benzyloxy derivatives of Ti IV were synthesized from Ti(iPrO) 4 using the alcoholysis route. These compounds were characterized using various analytical methods and single-crystal X-ray diffraction. Multinuclear NMR studies prove high degree of fluxional behavior of these compounds in solution. They adopt a dimeric structure in the solid state as seen from X-ray diffraction studies on a few of them. These compounds are powerful catalysts for the ring-opening polymerization of ε-caprolactone (CL) and δ-valerolactone (VL) resulting in high polymers with good number average molecular weights (M n ). Signifi-