reactivity of low valent Al(II) and Ga(II) complexes of the type (dpp-bian)M–M(dpp-bian) (1, M = Al; 2, Ga; dpp-bian2− = 1,2-bis-(2,6-iPr2-C6H3)-acenaphthenequinonediamido) with cyclic esters/carbonates such as ε-caprolactone (CL) and trimethylene carbonate (TMC). CL and TMC both readily coordinate to the Al(II) species 1 to form the corresponding bis-adducts (dpp-bian)Al(L)–(L)Al(dpp-bian) (3, L = CL; 4
本研究首先描述了(dpp-bian)M–M(dpp-bian)类型的低价Al(II)和Ga(II)配合物的反应性(1,M = Al; 2,Ga; dpp-bian 2-= 1,2-双-(2,6-iPr 2 -C 6 H 3)-ena
萘醌二酰胺基)与环状酯/
碳酸酯如
ε-己内酯(CL)和
碳酸三亚甲基酯(TMC)。CL和TMC都容易与Al(II)物种1形成相应的双加合物(dpp-bian)Al(L)–(L)Al(dpp-bian)(3,L = CL; 4,L = TMC),其结构特征证实了Al(II)-Al(II)双
金属主链在存在此类环状极性底物的情况下仍保持其完整性。相反,较少
路易斯酸的Ga(II)类似物2在室温下在
化学计算量的CL和TMC存在下没有反应。与BnOH结合使用时,双核Al(II)物种1是在室温下控制CL的ROP的极活泼的Al(II)
引发剂,胜过迄今为止报道的所有Al(III)同系