A series of organoaluminium imino-amido complexes of the type {[ArNC(Me2)C(Me)[double bond, length as m-dash]NAr]AlMe2} (Ar = 2,6-iPr2C6H3 (1), Ar = 2,6-Et2C6H3 (2); Ar = 2,6-Me2C6H3 (3) have been prepared via reaction of AlR3 and the respective α-diimine. Similar reaction of the bis(α-diimine) [ArN[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]N-]2 (Ar = 2,6-iPr2C6H3) with AlMe3 afforded the bimetallic complex [ArN-C(Me)2C(Me)[double bond, length as m-dash]NAlMe2]2 (4), whilst reaction of the acetyl-imino compound [O[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]NAr] (Ar = 2,6-Et2C6H3) with AlMe3 afforded the bimetallic complex {[OCMe2CH(Me)[double bond, length as m-dash]NAr]AlMe2}2 (5). In related organozinc chemistry, we have isolated {[ArNC(Me)(Et)C(Me)[double bond, length as m-dash]NAr]ZnEt} (Ar = 2,6-iPr2C6H3, 6) and the trinuclear complex {[ArN[double bond, length as m-dash]C(Me)COCHCO(Me)C(Me)[double bond, length as m-dash]NAr][OCH(Me)C(Me)[double bond, length as m-dash]NAr](ZnEt)3} (Ar = 2,6-iPr2C6H3, 7) from reactions of ZnEt2 with ArN[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]NAr or [O[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]NAr], respectively. Reaction of the bis(α-diimine), LiPr-N2-ArCH2Ar-N2, derived from 4,4'-methylenebis(2,6-diisopropylaniline), with ZnCl2 affords [LiPr-N2-ArCH2Ar-N2(ZnCl2)2] (8). The molecular structures of complexes 1-8 are reported. Preliminary results of the ability of 1-8, along with the previously reported metal-metal bonded complex {[ArN[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]NAr]Al(THF)}2 (9), to act as catalysts for the ring opening polymerization (ROP) of the cyclic esters ε-caprolactone (ε-CL), δ-valerolactone (δ-VL) and rac-lactide (r-LA) are presented. For ε-CL and δ-VL, best results were obtained using the metal-metal bonded complex 9. For r-LA, the Al-based systems exhibited moderate activity affording only liquid oligomers, whilst the Zn-based systems performed better affording at 80 °C isotactic PLA with Mnca. 10 kDa with conversions of up to 66%. The co-polymerization of ε-CL with δ-VL was also examined, and differing preferences were noted for monomer incorporation.

中文翻译：

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带有α-二亚胺和相关配体的单核和双核铝和锌配合物的合成，结构及其在环酯的开环聚合中的应用。

长度为m-NAR] ZnEt}（Ar = 2,6-iPr2C6H3，6）和三核配合物{[ArN [双键，长度为m-C]（Me）COCHCO（Me）C（Me） [双键，长度为m-破折号NAr] [OCH（Me）C（Me）[双键，长度为m-破折号NAr]（ZnEt）3}（Ar = 2,6-iPr2C6H3，7） ZnEt2与ArN [双键，长度为m-破折号C（Me）C（Me）[双键，长度为m-破折号NAr]或[O [双键，长度为m-破折号] C（Me C（Me）[双键，长度为m-NAr]。衍生自4,4'-亚甲基双（2,6-二异丙基苯胺）的双（α-二亚胺）LiPr-N2-ArCH2Ar-N2与ZnCl2反应得到[LiPr-N2-ArCH2Ar-N2（ZnCl2）2] （8）。报道了配合物1-8的分子结构。1-8能力的初步结果，以及先前报道的金属-金属键合复合物{[ArN [双键，长度为m-破折号] C（Me）C（Me）[双键，长度为m-NAr] Al（THF）} 2（9），用作环状酯ε-己内酯（ε-CL），δ-戊内酯（δ-VL）的开环聚合（ROP）催化剂）和外消旋丙交酯（r-LA）被提出。对于ε-CL和δ-VL，使用金属-金属键合配合物9可获得最佳结果。对于r-LA，基于Al的体系表现出中等的活性，仅提供液体低聚物，而基于Zn的体系表现出更好的活性，仅提供低聚物。 80°C等规PLA与Mnca。10 kDa，转换率高达66％。还检查了ε-CL与δ-VL的共聚作用，并指出了单体掺入的不同偏好。使用金属-金属键合配合物9可获得最佳结果。对于r-LA，Al基体系表现出中等活性，仅提供液体低聚物，而Zn基体系表现更好，在80°C等规PLA和Mnca条件下提供。10 kDa，转换率高达66％。还检查了ε-CL与δ-VL的共聚作用，并指出了单体掺入的不同偏好。使用金属-金属键合配合物9可获得最佳结果。对于r-LA，Al基体系表现出中等活性，仅提供液体低聚物，而Zn基体系表现更好，在80°C等规PLA和Mnca条件下提供。10 kDa，转换率高达66％。还检查了ε-CL与δ-VL的共聚作用，并指出了单体掺入的不同偏好。