(Arylimido)niobium(V)-Alkylidenes as the Catalysts for Ring Opening Metathesis Polymerization (ROMP) of Cyclic Olefins: Z-Specific ROMP of Cyclooctene by Nb(CHSiMe3)(NC6H5)[OC(CF3)3](PMe3)2
(Arylimido)niobium(V)-Alkylidenes as the Catalysts for Ring Opening Metathesis Polymerization (ROMP) of Cyclic Olefins: Z-Specific ROMP of Cyclooctene by Nb(CHSiMe3)(NC6H5)[OC(CF3)3](PMe3)2
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(芳基酰氨基)铌(V)-亚烷基作为环烯烃开环复分解聚合(ROMP)的催化剂：Nb(CHSiMe3)(NC6H5)[OC(CF3)3](PMe3)2对环辛烯的Z-特异性ROMP
DOI：
10.1021/acs.organomet.2c00665
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发表时间：
2023
期刊：
影响因子：
2.8
通讯作者：
K. Nomura
中科院分区：
文献类型：
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作者：
K. Chatchaipaiboon;K. Nomura
合成并鉴定了（芳基亚氨基）铌（V）-烷叉配合物Nb（CHSiMe 3）（NAr）[OC（CF 3）3]（PMe 3）2（Ar = C6 H5（4），2，6-F2 C6 H3，C6 F5（6）），Nb（CHSiMe 3）（N-2，6-Cl 2C 6 H3）（OC 6 F5）（PMe 3）2（7）和Nb（CHSiMe 3）（N-2，6-F2 C6 H3）（OC 6Cl 5）（PMe 3）2。五氟苯基亚氨基类似物6和7对异戊二烯的开环易位聚合（ROMP）表现出上级的催化活性（25 °C时TOF分别为56.1和53.7 s-1），在50 °C时活性增加（TOF ≥ 352 s-1）。所制备的亚烷基催化顺式环辛烯（COE）的开环易位聚合，在高温（80 °C）下活性增加。COE的Z-特异性ROMP已被证明，特别是通过苯基亚氨基类似物4在80 °C下，提供具有烯属双键的聚合物，具有排他性选择性（99%）。
(Arylimido)niobium(V)–alkylidene complexes, Nb(CHSiMe3)(NAr)[OC(CF3)3](PMe3)2(Ar = C6H5(4), 2,6-F2C6H3, C6F5(6)), Nb(CHSiMe3)(N-2,6-Cl2C6H3)(OC6F5)(PMe3)2(7), and Nb(CHSiMe3)(N-2,6-F2C6H3)(OC6Cl5)(PMe3)2, have been prepared and identified. The pentafluorophenylimido analogue6and7showed superior catalytic activities for the ring-opening metathesis polymerization (ROMP) of norbornene (TOF = 56.1, 53.7 s–1, respectively, at 25 °C) and the activities increased at 50 °C (TOF ≥ 352 s–1). The prepared alkylidenes catalyzed the ROMP ofcis-cyclooctene (COE), and the activity increased at high temperature (up to 80 °C). TheZ-specific ROMP of COE has been demonstrated especially by the phenylimido analogue4at 80 °C, affording polymers possessing olefinic double bonds with exclusivecisselectivity (99%).