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Synthesis of N-Methyl-o-phenylenediamine-Bridged Bis(phenolato) Lanthanide Alkoxides and Their Catalytic Performance for the (Co)Polymerization of rac-Butyrolactone and l-Lactide
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-06-18 , DOI: 10.1021/acs.inorgchem.2c00582 Tian Tian 1 , Chunping Feng 1 , Yaorong Wang 1 , Xuehua Zhu 2 , Dan Yuan 1 , Yingming Yao 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-06-18 , DOI: 10.1021/acs.inorgchem.2c00582 Tian Tian 1 , Chunping Feng 1 , Yaorong Wang 1 , Xuehua Zhu 2 , Dan Yuan 1 , Yingming Yao 1
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A series of lanthanide alkoxo complexes supported by ONNO salalen ligands were synthesized and characterized. A one-pot reaction of LH2 (L = (2-O–C6H2–tBu2-3,5)CH═N–C6H4–N(CH3)CH2(2-O–C6H2–tBu2-3,5)) with LnCp3(THF) in a 1:1 molar ratio followed by the addition of 1 equiv of ROH (R = Bn, iPr, and CF3CH2), afforded the dimeric lanthanide alkoxo complexes [LLn(μ-OCH2Ph)]2 [Ln = Lu (1), Yb (2), Sm (3), Nd (4)], [L2Yb(μ-OiPr)]2 (5), and [L2Yb(μ-OCH2CF3)]2 (6) in good isolated yields. All these lanthanide complexes were characterized by elemental analysis and FT-IR spectroscopy. In addition, complex 1 has been characterized by NMR spectroscopy. Single-crystal X-ray diffraction analysis of complexes 1, 2, 5, and 6 showed that these lanthanide alkoxo complexes are dimeric in the solid state. Complexes 1–6 showed good activity toward the homopolymerization of rac-butyrolactone (rac-BBL) to give atactic PHB, and ionic radii of central metals have profound influence on the polymerization. The polymerization behavior of l-lactide (l-LA) initiated by complex 2 was also explored. The kinetic study revealed that the polymerizations of rac-BBL and l-LA initiated by salalen lanthanide akoxide are first order for both the monomer and the initiator concentrations. Furthermore, it was found that complexes 1 and 2 showed good activity in the copolymerization of l-LA and rac-BBL, affording gradient copolymers.
中文翻译：
N-甲基邻苯二胺桥联双(苯酚)镧系醇盐的合成及其对外消旋丁内酯和L-丙交酯(共)聚合的催化性能
合成并表征了一系列由 ONNO salalen 配体支持的镧系烷氧基配合物。LH 2 (L = (2-O–C 6 H 2 – t Bu 2 -3,5)CH=N–C 6 H 4 –N(CH 3 )CH 2 (2-O– C 6 H 2 – t Bu 2 -3,5)) 与 LnCp 3 (THF) 的摩尔比为 1:1，然后添加 1 equiv 的 ROH（R = Bn、i Pr 和 CF 3 CH 2） , 得到二聚镧系烷氧基配合物 [LLn(μ-OCH 2 Ph)]2 [Ln = Lu ( 1 )、Yb ( 2 )、Sm ( 3 )、Nd ( 4 )]、[L 2 Yb(μ-O i Pr)] 2 ( 5 ) 和 [L 2 Yb(μ- OCH 2 CF 3 )] 2 ( 6 ) 具有良好的分离产率。所有这些镧系元素配合物都通过元素分析和 FT-IR 光谱进行了表征。此外，配合物1已通过 NMR 光谱进行了表征。配合物1、2、5和6的单晶X 射线衍射分析表明这些镧系元素烷氧基配合物在固态下是二聚体。配合物1-6对外消旋丁内酯 ( rac - BBL)的均聚反应生成无规 PHB 表现出良好的活性，并且中心金属的离子半径对聚合具有深远的影响。还探讨了络合物2引发的l-丙交酯( l -LA)的聚合行为。动力学研究表明，由 salalen lanthanide akoxide 引发的rac -BBL 和l -LA 的聚合对于单体和引发剂浓度都是一级反应。此外，还发现配合物1和2在l -LA 和rac -BBL的共聚中表现出良好的活性，提供梯度共聚物。
更新日期：2022-06-18
中文翻译：
N-甲基邻苯二胺桥联双(苯酚)镧系醇盐的合成及其对外消旋丁内酯和L-丙交酯(共)聚合的催化性能
合成并表征了一系列由 ONNO salalen 配体支持的镧系烷氧基配合物。LH 2 (L = (2-O–C 6 H 2 – t Bu 2 -3,5)CH=N–C 6 H 4 –N(CH 3 )CH 2 (2-O– C 6 H 2 – t Bu 2 -3,5)) 与 LnCp 3 (THF) 的摩尔比为 1:1，然后添加 1 equiv 的 ROH（R = Bn、i Pr 和 CF 3 CH 2） , 得到二聚镧系烷氧基配合物 [LLn(μ-OCH 2 Ph)]2 [Ln = Lu ( 1 )、Yb ( 2 )、Sm ( 3 )、Nd ( 4 )]、[L 2 Yb(μ-O i Pr)] 2 ( 5 ) 和 [L 2 Yb(μ- OCH 2 CF 3 )] 2 ( 6 ) 具有良好的分离产率。所有这些镧系元素配合物都通过元素分析和 FT-IR 光谱进行了表征。此外，配合物1已通过 NMR 光谱进行了表征。配合物1、2、5和6的单晶X 射线衍射分析表明这些镧系元素烷氧基配合物在固态下是二聚体。配合物1-6对外消旋丁内酯 ( rac - BBL)的均聚反应生成无规 PHB 表现出良好的活性，并且中心金属的离子半径对聚合具有深远的影响。还探讨了络合物2引发的l-丙交酯( l -LA)的聚合行为。动力学研究表明，由 salalen lanthanide akoxide 引发的rac -BBL 和l -LA 的聚合对于单体和引发剂浓度都是一级反应。此外，还发现配合物1和2在l -LA 和rac -BBL的共聚中表现出良好的活性，提供梯度共聚物。
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