Synthesis and Characterization of Dialkylaluminum Amidates and Their Ring-Opening Polymerization of 蔚-Caprolactone

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• 作者：Wenjuan Zhang ; Youhong Wang ; Ji Cao ; Lin Wang ; Yi Pan ; Carl Redshaw ; Wen-Hua Sun
• 刊名：Organometallics
• 出版年：2011
• 出版时间：November 28, 2011
• 年：2011
• 卷：30
• 期：22
• 页码：6253-6261
• 全文大小：413K
• 年卷期：v.30,no.22(November 28, 2011)
• ISSN：1520-6041

文摘

The stoichiometric reactions of N-(2-methylquinolin-8-yl) (R)amides (L1鈥?b>L8; L1, R = Ph; L2, R = p-FPh; L3, R = p-ClPh; L4, R = p-(MeO)Ph; L5, R = o-MePh; L6, R = p-MePh; L7, R = Me; L8, R = CF₃) with Me₃Al afforded the corresponding dimethylaluminum amidate complexes [Me₂AlL] (C1鈥?b>C8). The treatment of N-(2-methylquinolin-8-yl)picolinamide (L9) with 1 or 2 equiv of Me₃Al formed Me₂AlL9 (C9) or Me₂AlL9路Me₃Al (C10), respectively; meanwhile, the stoichiometric reaction of L9 with iBu₃Al gave iBu₂AlL9 (C11). All organoaluminum amidate complexes were fully characterized by ¹H/¹³C NMR spectroscopy and elemental analysis, and the unambiguous structures of complexes C2, C4, C9, and C11 were further determined by single-crystal X-ray diffraction. With the assistance of 1 equiv of BnOH, all dialkylaluminum amidate complexes showed appreciable activities toward the ring-opening polymerization of 蔚-caprolactone and produced polycaprolactones with narrow polydispersity; the nature of the active species was also investigated.