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The reaction of the highly sterically demanding NNN'-heteroscorpionate protioligands pbp  amd-H, tbp  amd-H, and phbp  amd-H (a) and the low sterically hindered analogs pbpamd-H, tbpamd-H, and phbpamd-H (b), with 1 equiv of AlR 3 (R = Me, Et) proceed in high yields to give two families of complexes: the mononuclear dialkyl aluminum bidentate-acetamidinates [AlR 2 (κ 2 - N' N')] (κ 2 - N' N' = pbp  amd, R = Me 1, Et 2; tbp  amd, R = Me 3, Et 4; phbp  amd, R = Me 5, Et 6) and the monodentate-acetamidinates [AlR 2 (κ 2 - NN')] (κ 2 - NN' = tbpamd, R = Me 7; phbpamd, R = Me 8, Et 9). In complexes 7-9, the presence of two possible CH-NH tautomers as low extended π-N-C-N'(sp 2 )-Al and high extended π-HN-C 2 -N'(sp 2 )-Al complexes, respectively, could be identified. Moreover, the reaction of aluminum dimethyls 7 and 8 with ZnMe 2 afforded the isolation of the more stable scorpionate zinc monoalkyls [Zn(Me)(κ 3 - NNN')] ( NNN' = tbpamd 10 and phbpamd 11), through a very unusual ligand exchange process, involving a zinc-to-aluminum transmetalation of an alkyl group. The X-ray crystal structures of 1, 3, 7, and 8, as well as that of 11, confirmed unambiguously the different κ 2 -arrangements proposed for bi- or monodentate acetamidinate dialkyls 1-6 and 7-9, respectively, the presence of NH tautomer in 7 and 8, and a κ 3 - NNN' coordination in monoalkyl 11. Density functional theory calculations were used to explore the three different favored κ 2 -arrangements found in acetamidinate aluminum dialkyls 1-9, the relative stability of both CH-NH tautomers, and the ligand transfer reaction leading to the formation of κ 3 - NNN' zinc monoalkyls 10 and 11. Interestingly, dialkyls 1, 5, 7, and 8 can act as highly efficient single-component living initiators for the ring-opening polymerization of ε-caprolactone and rac-lactide in mild conditions after hours. These initiators efficiently mediated the immortal polymerization in the presence of excess of benzyl alcohol (up to 20 equiv), as evidenced by the narrow dispersity values and the good agreement between the experimental M n values and monomer/benzyl alcohol ratios. In addition, the most sterically hindered initiator, 5, exhibits enhanced levels of heteroselectivity on the produced PLAs, reaching P s values up to 0.70.

Organo-Aluminum and Zinc Acetamidinates: Preparation, Coordination Ability, and Ring-Opening Polymerization Processes of Cyclic Esters