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Methylene-Bridged Bisphosphine Monoxide Ligands for Palladium-Catalyzed Copolymerization of Ethylene and Polar Monomers
ACS Macro Letters ( IF 5.1 ) Pub Date : 2018-02-16 00:00:00 , DOI: 10.1021/acsmacrolett.8b00034 Yusuke Mitsushige 1 , Hina Yasuda 1 , Brad P Carrow 2 , Shingo Ito 1 , Minoru Kobayashi 3 , Takao Tayano 3 , Yumiko Watanabe 4 , Yoshishige Okuno 4 , Shinya Hayashi 5 , Junichi Kuroda 5 , Yoshikuni Okumura 5 , Kyoko Nozaki 1
ACS Macro Letters ( IF 5.1 ) Pub Date : 2018-02-16 00:00:00 , DOI: 10.1021/acsmacrolett.8b00034 Yusuke Mitsushige 1 , Hina Yasuda 1 , Brad P Carrow 2 , Shingo Ito 1 , Minoru Kobayashi 3 , Takao Tayano 3 , Yumiko Watanabe 4 , Yoshishige Okuno 4 , Shinya Hayashi 5 , Junichi Kuroda 5 , Yoshikuni Okumura 5 , Kyoko Nozaki 1
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A series of palladium complexes bearing a bisphosphine monoxide with a methylene linker, that is, [κ2-P,O-(R12P)CH2P(O)R22]PdMe(2,6-lutidine)][BArF4] (Pd/BPMO), were synthesized and evaluated as catalysts for the homopolymerization of ethylene and the copolymerization of ethylene and polar monomers. X-ray crystallographic analyses revealed that these Pd/BPMO complexes exhibit significantly narrower bite angles and longer Pd–O bonds than Pd/BPMO complexes bearing a phenylene linker, while maintaining almost constant Pd–P bond lengths. Among the complexes synthesized, menthyl-substituted complex 3f (R1 = (1R,2S,5R)-2-isopropyl-5-methylcyclohexan-1-yl; R2 = Me) showed the best catalytic performance in the homo- and copolymerization in terms of molecular weight and polymerization activity. Meanwhile, complex 3e (R1 = t-Bu; R2 = Me) exhibited a markedly higher incorporation of comonomers in the copolymerization of ethylene and allyl acetate (≤12.0 mol %) or methyl methacrylate (≤0.6 mol %). The catalytic system represents one of the first examples of late-transition-metal complexes bearing an alkylene-bridged bidentate ligand that afford high-molecular-weight copolymers from the copolymerization of ethylene and polar monomers.
中文翻译：
用于钯催化乙烯和极性单体共聚的亚甲基桥连一氧化二膦配体
一系列带有二氧化膦和亚甲基接头的钯配合物，即[κ 2 - P , O -(R 1 2 P)CH 2 P(O)R 2 2 ]PdMe(2,6-lutidine)] [BAr F 4 ] (Pd/BPMO) 作为乙烯均聚和乙烯与极性单体共聚的催化剂进行了合成和评价。X 射线晶体学分析表明，与带有亚苯基接头的 Pd/BPMO 配合物相比，这些 Pd/BPMO 配合物表现出明显更窄的咬合角和更长的 Pd-O 键，同时保持几乎恒定的 Pd-P 键长。在合成的配合物中，薄荷基取代的配合物3f(R 1 = (1 R ,2 S ,5 R )-2-isopropyl-5-methylcyclohexan-1-yl; R 2 = Me)在均聚和共聚中的分子量和聚合反应中表现出最好的催化性能活动。同时，配合物3e (R 1 = t -Bu; R 2= Me) 在乙烯和乙酸烯丙酯 (≤12.0 mol%) 或甲基丙烯酸甲酯 (≤0.6 mol%) 的共聚中表现出显着更高的共聚单体掺入。该催化体系代表了具有亚烷基桥联双齿配体的后过渡金属配合物的第一个例子，该配合物由乙烯和极性单体的共聚提供高分子量共聚物。
更新日期：2018-02-16
中文翻译：
用于钯催化乙烯和极性单体共聚的亚甲基桥连一氧化二膦配体
一系列带有二氧化膦和亚甲基接头的钯配合物，即[κ 2 - P , O -(R 1 2 P)CH 2 P(O)R 2 2 ]PdMe(2,6-lutidine)] [BAr F 4 ] (Pd/BPMO) 作为乙烯均聚和乙烯与极性单体共聚的催化剂进行了合成和评价。X 射线晶体学分析表明，与带有亚苯基接头的 Pd/BPMO 配合物相比，这些 Pd/BPMO 配合物表现出明显更窄的咬合角和更长的 Pd-O 键，同时保持几乎恒定的 Pd-P 键长。在合成的配合物中，薄荷基取代的配合物3f(R 1 = (1 R ,2 S ,5 R )-2-isopropyl-5-methylcyclohexan-1-yl; R 2 = Me)在均聚和共聚中的分子量和聚合反应中表现出最好的催化性能活动。同时，配合物3e (R 1 = t -Bu; R 2= Me) 在乙烯和乙酸烯丙酯 (≤12.0 mol%) 或甲基丙烯酸甲酯 (≤0.6 mol%) 的共聚中表现出显着更高的共聚单体掺入。该催化体系代表了具有亚烷基桥联双齿配体的后过渡金属配合物的第一个例子，该配合物由乙烯和极性单体的共聚提供高分子量共聚物。
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