Abstract: | The reaction of 2‐methoxybenzyl alcohol with one molar equiv of R2AIX in diethyl ether at 0°C gives (2‐MeOC6H4CH2‐μ‐O)AlRX]2 ( 1 : R = Et, X = Cl, 2 : R = X = Et). In addition, 2,4‐di‐tert‐butylphenol reacts with iBu3Al affording a four‐coordinated aluminum compound (μ‐2,4‐tBu2‐C6H4O)Al(iBu)2]2 ( 4 ). Single crystal X‐ray structure analysis of 4 shows a C2h‐symmetry with a planar Al2O2 core. Ring‐opening polymerization (ROP) of caprolactones initiated by 1, 4 and (μ‐OCH2C6H4OMe)Al(iBu)2]2 ( 3 ) is performed and polyesters with narrow molecular weight distributions were obtained from the “living” ROP of caprolactones. 1H NMR spectroscopic studies of PCL reveal that the initiator of 1 and 3 is through the Al‐OAr function, but the initiator of 4 is through the Al‐ iBu group. |