Acenaphthylenebisamido metal complexes (dpp-bian)Mg(thf)₃ and (dpp-bian)Ca(thf)₄ by reaction with azobenzene and dicumyl peroxide, respectively, give paramagnetic species [(dpp-bian)Mg(thf)NPh]₂ (3) and (dpp-bian)CaOCMe₂Ph(dme) (4) containing monoanionic dpp-bian ligand. Treating the parent compounds with 1 equiv of 2,6-di-tert-butyl-4-methylphenol leads to formation of amino/amidoacenaphthylene-supported complexes (dpp-bianH)MgO(^tBu₂MeC₆H₂)(thf) (5) and (dpp-bianH)CaO(^tBu₂MeC₆H₂)(thf)₂ (6) featuring ancillary bulky phenoxido ligand. As NMR studies confirm, a sterically demanding moiety in the magnesium coordination sphere hinders the intramolecular shuttle proton transfer in 5, whereas calcium complex 6 maintains typical dynamics in solution. Compounds obtained show a modest activity in ROP of L-lactide in toluene. In particular, 3 and 4 prove to be active for moderate-controlled polymerization, whereas 5 and 6 give broadly dispersed PLAs.

通过分别与偶氮苯和过氧化二枯基反应，亚甲基双酰胺金属配合物（dpp-bian）Mg（thf）₃和（dpp-bian）Ca（thf）₄产生顺磁性物质[（dpp-bian）Mg（thf）NPh] ₂（3）和包含单阴离子dpp-bian配体的（dpp-bian）CaOCMe ₂ Ph（dme）（4）。用1当量的2,6-二叔丁基-4-甲基苯酚处理母体化合物会形成氨基/ ami并ena撑的配合物（dpp-bianH）MgO（^t Bu ₂ MeC ₆ H ₂）（thf）（5）和（dpp-bianH）CaO（^t Bu ₂ MeC ₆ H₂）（thf）₂（6）的特征是辅助的庞大的苯氧基配体。正如NMR研究所证实的，镁配位球中的空间需求部分阻碍了分子内穿梭质子在5中的转移，而钙络合物6在溶液中保持了典型的动力学。获得的化合物在甲苯中的L-丙交酯的ROP中显示适度的活性。特别是，3和4被证明对中度控制的聚合反应有活性，而5和6则可得到广泛分散的PLA。