Pd-Iminocarboxylate Complexes and Their Behavior in Ethylene Polymerization.,Chemistry - An Asian Journal

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Pd-Iminocarboxylate Complexes and Their Behavior in Ethylene Polymerization.
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2019-12-21 , DOI: 10.1002/asia.201901501
Satej S Deshmukh ₁ , Shahaji R Gaikwad ₁ , Rajesh G Gonnade ₂ , Satish P Pandole ₃ , Samir H Chikkali _{1,

4}

Affiliation

Designing co-catalyst-free late transition metal complexes for ethylene polymerization is a challenging task at the interface of organometallic and polymer chemistry. Herein, a set of new, co-catalyst-free, single-component catalytic systems for ethylene polymerization have been unraveled. Treatment of anthranilic acid with various aldehydes produced four iminocarboxylate ligands (L1-L4) in very good to excellent yield (75-92 %). The existence of 2-((2-methoxybenzylidene)amino) benzoic acid (L1) has been unambiguously demonstrated using NMR spectroscopy, MS and single-crystal X-ray diffraction. A neutral Pd-iminocarboxylate complex [{N O}PdMe(L1)] (N O=κ2 -N,O-ArCHNC6 H4 CO2 with Ar=2-MeOC6 H4 ) C1 was prepared by treating stoichiometric amount of L1.Na with palladium precursor. The identity of C1 was confirmed by 1-2D NMR spectroscopy and single-crystal X-ray diffraction studies. Along the same lines, palladium complexes C2-C4 were prepared from ligands L2-L4 respectively. In-situ high-pressure NMR investigations revealed that these Pd complexes are amenable to ethylene insertion and undergo facile β-H elimination to produce propylene. These palladium complexes were then evaluated in ethylene polymerization reaction and various reaction parameters were screened. When C1-C4 were exposed to ethylene pressures of 10-50 bar, formation of low-molecular-weight polyethylene was observed.

中文翻译：

Pd-氨基羧酸盐配合物及其在乙烯聚合中的行为。

在有机金属和聚合物化学的界面上，设计用于乙烯聚合的无助催化剂的后期过渡金属配合物是一项艰巨的任务。在此，已经阐明了一套用于乙烯聚合的新的无助催化剂的单组分催化体系。用各种醛处理邻氨基苯甲酸产生了四个亚氨基羧酸酯配体（L1-L4），非常好至极佳的收率（75-92％）。使用NMR光谱法，MS和单晶X射线衍射已明确证明了2-（（2-甲氧基亚苄基）氨基）苯甲酸（L1）的存在。通过用钯前体处理化学计量的L1.Na，制备了中性的Pd-亚氨基羧酸盐配合物[{N}} PdMe（L1）]（N O =κ2-N，O-ArCHNC6 H4 CO2和Ar = 2-MeOC6 H4）C1。通过1-2D NMR光谱和单晶X射线衍射研究确认了C1的身份。同样，分别从配体L2-L4制备钯配合物C2-C4。原位高压NMR研究表明，这些Pd配合物易于插入乙烯，并易于β-H消除生成丙烯。然后在乙烯聚合反应中评估这些钯配合物，并筛选各种反应参数。当C1-C4暴露于10-50巴的乙烯压力下时，观察到低分子量聚乙烯的形成。原位高压NMR研究表明，这些Pd配合物适合乙烯插入，并易于β-H消除生成丙烯。然后在乙烯聚合反应中评估这些钯配合物，并筛选各种反应参数。当C1-C4暴露于10-50巴的乙烯压力下时，观察到低分子量聚乙烯的形成。原位高压NMR研究表明，这些Pd配合物适合乙烯插入，并易于β-H消除生成丙烯。然后在乙烯聚合反应中评估这些钯配合物，并筛选各种反应参数。当C1-C4暴露于10-50巴的乙烯压力下时，观察到低分子量聚乙烯的形成。

更新日期：2020-01-16

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