Department of Chemistry, Faculty of Science and Engineering, Tokyo Metropolitan University , 1-1 Minami Osawa, Hachioji, Tokyo 192-0397, Japan.
J Am Chem Soc. 2016 Sep 14;138(36):11840-9. doi: 10.1021/jacs.6b06330. Epub 2016 Aug 29.
Ring-opening metathesis polymerization (ROMP) of various cyclic olefins especially using three (arylimido)vanadium(V)-alkylidene catalysts, V(CHSiMe3)(N-2,6-Cl2C6H3) (OC6F5) (PMe3)2 (3), V(CHSiMe3) (NR)OC(CF3)32 [R = Ph (6), 2,6-Cl2C6H3 (7)] have been explored. Complex 3 exhibited the highest catalytic activity (ex. TOF = 603 000 h(-1), 168 s(-1)) for ROMP of norbornene (NBE) among a series of (imido)vanadium(V)-alkylidenes, and the cis-specific living ROMPs of NBE proceeded with remarkable activities (TOF = 125 000-157 000 h(-1) at 25 °C) by the fluorinated alkoxo analogues (6, 7). The activities by 6, 7 increased at high temperature (50 and 80 °C) and/or upon addition of PMe3 without decrease in the cis selectivity (98%). The ROMPs in the presence of 1-hexene by 3, 7 proceeded without significant decrease in the activities, and the Mn values could be controlled by degree of chain transfer (cross metathesis). These dichlorophenylimido analogues (3, 7) were effective for ROMPs of various norbornene derivatives; ROMP of cyclooctene took place by 3, and the activity increased at high temperature (50, 80 °C).
各种环烯烃，尤其是使用三（芳基亚氨基）钒（V）-亚烷基催化剂的开环易位聚合（ROMP），V（CHSiMe3）（N-2,6-Cl2C6H3）（OC6F5）（PMe3）2（3），V（CHSiMe3）（NR）[OC（CF3）3]（PMe3）2 [R = Ph（6），2,6-Cl2C6H3（7）]，已经被探索。复合物 3 在一系列（亚氨基）钒（V）-亚烷基中表现出最高的降冰片烯（NBE）ROMP 催化活性（例如，TOF = 603 000 h（-1），168 s（-1）），而 NBE 的顺式特异性活 ROMP 通过氟化烷氧基类似物（6,7）以显著的活性进行（在 25°C 时，TOF = 125 000-157 000 h（-1））。在高温（50 和 80°C）和/或添加 PMe3 时，6,7 的活性增加，而顺式选择性没有降低（98%）。在 3、7 的存在下，通过 1-己烯的 ROMP 活性没有明显降低，并且 Mn 值可以通过链转移（交叉易位）的程度来控制。这些二氯苯基亚氨基类似物（3,7）对各种降冰片烯衍生物的 ROMP 有效；3 进行环辛烯的 ROMP，并且在高温（50、80°C）下活性增加。
