title: Geometry Constrained N-(5,6,7-Trihydroquinolin-8-ylidene)arylaminopalladium Dichloride Complexes: Catalytic Behavior toward Methyl Acrylate (MA), Methyl Acrylate-co-Norbornene (MA-co-NB) Polymerization and Heck Coupling.
abstract: A new pair of plladium complexes (Pd4andPd5) ligated with constrainedN-(5,6,7-trihydroquinolin-8-ylidene)arylamine ligands have been prepared and well characterized by ¹H-,13C-NMR and FTIR spectroscopies as well as elemental analysis. The molecular structure ofPd4andPd5in solid state have also been determined by X-ray diffraction, showing slightly distorted square planar geometry around the palladium metal center. All complexesPd1-Pd5are revealed highly efficient catalyst in methyl acrylate (MA) polymerization as well as methyl acrylate/norbornene (MA/NB) copolymerization. In the case of MA polymerization, as high as 98.4% conversion with high molecular weight up to 6282 kg·mol-1was achieved. Likewise,Pd3complex has good capability to incorporate about 18% NB content into MA polymer chains. Furthermore, low catalyst loadings (0.002 mol %) ofPd4orPd5are able to efficiently mediate the coupling of haloarenes with styrene affording up to 98% conversion.
authors.affiliation: Key Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. ynzeng@iccas.ac.cn.|State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China. ynzeng@iccas.ac.cn.
authors.forename: Yanning
authors.initials: Y
authors.lastname: Zeng
authors.affiliation: Key Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. mqaiser@iccas.ac.cn.|International School, University of Chinese Academy of Sciences, Beijing 100049, China. mqaiser@iccas.ac.cn.
authors.forename: Qaiser
authors.initials: Q
authors.lastname: Mahmood
authors.affiliation: Key Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. ltl@iccas.ac.cn.
authors.forename: Tongling
authors.initials: T
authors.lastname: Liang
authors.affiliation: Key Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. whsun@iccas.ac.cn.|State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China. whsun@iccas.ac.cn.|International School, University of Chinese Academy of Sciences, Beijing 100049, China. whsun@iccas.ac.cn.
authors.forename: Wen-Hua
authors.initials: WH
authors.lastname: Sun
mesh_terms: D000179:Acrylates / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009636:Norbornanes / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D013237:Stereoisomerism; D014961:X-Ray Diffraction
chemical_list: D000179:Acrylates; D009636:Norbornanes; D011108:Polymers; C046060:2-norbornene; D010165:Palladium; C035956:methyl acrylate
keywords: Heck coupling; MA/NB copolymerization; constrained ligand framework; homopolymerization of MA; palladium complexes