Lithium complexes supported by amine bis-phenolate ligands as efficient catalysts for ring-opening polymerization of L-lactide

Huang CA; Chen CT

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Lithium complexes supported by amine bis-phenolate ligands as efficient catalysts for ring-opening polymerization of L-lactide

机译：胺双酚盐配体负载的锂络合物作为L-丙交酯开环聚合的有效催化剂

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Lithium complexes bearing dianionic amine bis( phenolate) ligands are described. Reactions of ligand precursors H2O2NNMe, H2O2NNPy or H2O2NOMe [H2O2NNMe = Me2NCH2CH2N-(CH2-2-HO-3, 5-C6H2(Bu-t)(2))(2); H2O2NNPy = (2-C5H4N)CH2N-(CH2-2-HO-3,5-C6H2(Bu-t)(2))(2); H2O2NOMe = MeOCH2CH2N-(CH2-2-HO-3,5-C6H2(Bu-t)(2))(2)] with 2.2 molar equivalents of (BuLi)-Bu-n in diethylether afford (Li2O2NNMe) 2 (1), (Li2O2NNPy)(2)(2) and (Li2O2NOMe)(2) (3) as tetra-nuclear lithium complexes. The crystalline solids of partially hydrolyzed product, (LiO(HO)NNPy) (4), were obtained from recrystallization of 2 in diethylether solution for three months. The synthesis of (LiO(HO)NOMe)(2) (5) was carried out at ambient temperature by carefully layering a solution of water in hexane on top of a solution of 3 in Et2O. Crystalline solids of 5 were obtained after two months. Molecular structures are reported for compounds 1, 3, 4 and 5. Compounds 1-3 show excellent catalytic activities toward the ring-opening polymerization of L-lactide in the presence of benzyl alcohol.

机译：描述了带有双阴离子双（酚盐）配体的锂配合物。配体前体H 2 O 2 NNMe，H 2 O 2 NNPy或H 2 O 2 NOMe的反应[H 2 O 2 NNMe ＝ Me 2 NCH 2 CH 2 N-（CH 2-2-HO-3，5-C 6 H 2（Bu-t）（2））（2）; H 2 O 2 NNMe。 H2O2NNPy =（2-C5H4N）CH2N-（CH2-2-HO-3,5-C6H2（Bu-t）（2））（2）; H2O2NOMe = MeOCH2CH2N-（CH2-2-HO-3,5-C6H2（Bu-t）（2））（2）]，在乙醚中具有2.2摩尔当量的（BuLi）-Bu-n，得到（Li2O2NNMe）2（1 ），（Li2O2NNPy）（2）（2）和（Li2O2NOMe）（2）（3）作为四核锂配合物。部分水解产物（LiO（HO）NNPy）（4）的结晶固体是从2在乙醚溶液中重结晶三个月获得的。（LiO（HO）NOMe）（2）（5）的合成是在环境温度下，通过小心地将水在己烷中的溶液分层放在3在Et2O中的溶液之上而进行的。两个月后获得5的结晶固体。报道了化合物1、3、4和5的分子结构。化合物1-3在苄醇存在下对L-丙交酯的开环聚合反应显示出优异的催化活性。

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《Dalton transactions: An international journal of inorganic chemistry》 |2007年第47期|共6页
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Huang CA; Chen CT;
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正文语种 eng
中图分类无机化学;
关键词
GROUP-3 METAL-COMPLEXES; EPSILON-CAPROLACTONE; CYCLIC ESTERS; LANTHANIDE COMPLEXES; ZIRCONIUM COMPLEXES; YTTRIUM INITIATORS; ALUMINUM; TITANIUM; REACTIVITY; POLYMERS;

机译：第3组金属络合物;ε-己内酯;环酯;镧系元素络合物;锆络合物;钇引发剂;铝;钛;反应性;聚合物;

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专利

1. Lithium complexes supported by amine bis-phenolate ligands as efficient catalysts for ring-opening polymerization of L-lactide [J] . Huang CA, Chen CT Dalton transactions: An international journal of inorganic chemistry . 2007,第47期

机译：胺双酚盐配体负载的锂络合物作为L-丙交酯开环聚合的有效催化剂
2. Aluminium metal complexes supported by amine bis-phenolate ligands as catalysts for ring-opening polymerization of ε-caprolactone [J] . Chi-Tien Chen, Chi-An Huang, Bor-Hunn Huang Dalton transactions: An international journal of inorganic chemistry . 2003,第19期

机译：胺双酚盐配体负载的铝金属配合物作为ε-己内酯开环聚合的催化剂
3. Synthesis, structural characterization and reactivity of aluminium complexes supported by benzotriazole phenoxide ligands: Air-stable alumoxane as an efficient catalyst for ring-opening polymerization of l-lactide [J] . Li C.-Y., Tsai C.-Y., Lin C.-H., Dalton transactions: An international journal of inorganic chemistry . 2011,第9期

机译：苯并三唑酚盐配体负载的铝配合物的合成，结构表征和反应活性：空气稳定的铝氧烷作为l-丙交酯开环聚合的有效催化剂
4. Complexes of Amine Phenolate Ligands as Catalysts for Polymerization of α-Olefins [C] . Moshe Kol, Edit Y. Tshuva, Zeev Goldschmidt Symposium on beyond metallocenes: Next-generation polymerization catalysts . 2003

机译：胺酚酸配体作为α-烯烃聚合的催化剂
5. Chemistry of Magnesium and Zinc Complexes Supported by Bulky Ancillary Ligands and their Applications in the Ring-Opening Polymerization Studies of Cyclic Esters. [D] . Wambua, Pasco M. 2014

机译：大体积辅助配体支持的镁和锌配合物的化学及其在环酯开环聚合研究中的应用。
6. Zinc Complexes Containing Coumarin-Derived Anilido-Aldimine Ligands as Catalysts for Ring Opening Polymerization of l-Lactide [O] . Chi-Tien Chen, Min-Chian Wang, Tzu-Lun Huang 2015

机译：含香豆素衍生的苯胺-醛亚胺配体的锌配合物作为l-丙交酯开环聚合的催化剂
7. Synthesis and characterization of bisphenol sodium complexes: An efficient catalyst for the ring-opening polymerization of L-lactide [O] . Xu, Xianrui, Pan, Xiaobo, Tang, Sifu, 2013

机译：双酚钠配合物的合成与表征：L-丙交酯开环聚合的有效催化剂
8. Preparation and Reactions of Tantalum Alkylidene Complexes Containing Bulky Phenoxide or Thiolate Ligands. Controlling Ring-Opening Metathesis Polymerization Activity and Mechanism Through Choice of Anionic Ligand [R] . Wallace, K. C., Liu, A. H., Dewan, J. C., 1988

机译：含大量酚盐或硫醇盐配体的亚钽基亚砜配合物的制备及反应。通过选择阴离子配体控制开环易位聚合活性及机理

Lithium complexes supported by amine bis-phenolate ligands as efficient catalysts for ring-opening polymerization of L-lactide

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