A series of new bisphosphine-monoxide (BPMO) ligands based on benzothiophene backbone and the corresponding palladium complexes {K²-2-P(O)(Ph)₂-3-PR¹R²-C₈H₄S}PdMeCl {2a: R¹ = R² = Ph; 2b: R¹ = R² = 2-OMe-Ph; 2c: R¹ = R² = 2-CF₃-Ph; 2d: R¹ = Ph, R² = 2-(2′,6′-(OMe)₂C₆H₃)-C₆H₄} were synthesized and fully characterized by 1 H-, ¹³C-, ³¹P-, and 2D-NMR spectroscopy and single-crystal X-ray diffraction. In the presence of Na⁺B[3,5-(CF₃)₂C₆H₃]₄₋ (NaBArF), these complexes showed very high activities (up to 2.0 × 10⁷ gmo⁻¹·h⁻¹) for ethylene polymerization. More significantly, these catalysts enabled the copolymerization of ethylene with a broad scope of commercially available polar comonomers such as acrylates, acrylic acid, acrylonitrile, vinyltrialkoxysilane, allyl acetate, and long-chain 6-chloro-1-hexene to give functionalized polyethylene with reasonable catalytic activities (up to 10⁶ g·mol⁻¹·h⁻¹) and incorporations (up to 5.3 mol%). This contribution suggests that, besides the modulation of conventionally steric and electronic factors, the connectivity (at different linking positions) of BPMO (P,O) donors to the heteroaryl backbone also greatly influences the catalyst properties in terms of catalytic activity, polymer branching content, comonomer scope, and comonomer incorporation.

基于苯并噻吩骨架和相应的钯配合物{K ² -2-P（O）（Ph）₂ -3-PR ¹ R ² -C ₈ H ₄ S} PdMeCl {} 2a：R ¹＝ R ²＝ Ph；2b：R ¹＝ R ²＝ 2-OMe-Ph；2c：R ¹＝ R ²＝ 2-CF ₃ -Ph；2d：R ¹＝ Ph，R ²＝ 2-（2′，6′-（OMe）₂ C ₆ H ₃）-C合成了₆ H ₄ }，并通过1 H-，¹³ C-，³¹ P-和2D-NMR光谱和单晶X射线衍射进行了全面表征。在Na ⁺ B [3,5-（CF ₃）₂ C ₆ H ₃ ] _4-（NaBArF）的存在下，这些络合物显示出非常高的活性（高达2.0×10 ⁷ gmo ^-1 ·h ^-1）用于乙烯聚合。更重要的是，这些催化剂能够使乙烯与广泛的市售极性共聚单体（例如丙烯酸酯，丙烯酸，丙烯腈，乙烯基三烷氧基硅烷，乙酸烯丙酯和长链6-氯-1-己烯）进行共聚，从而得到合理的官能化聚乙烯催化活性（高达10 ⁶ g·mol ^-1 ·h ^-1）和掺入量（最高5.3 mol％）。该贡献表明，除了调节常规的空间和电子因素外，BPMO（P，O）供体与杂芳基主链的连接性（在不同的连接位置）也极大地影响了催化剂的催化活性，聚合物支化含量等性能。 ，共聚单体范围和共聚单体掺入。