Selective Ring-Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation

Neary William J.; Sun Yunyan; Moore Jeffrey S.

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Selective Ring-Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation

机译：选择性环开口联合鼻甲：聚合或钌亚乙烯基形成

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Selective ring-opening allene metathesis polymerization (ROAlMP) and ruthenium vinylidene formation from 1,2-cyclononadiene (1) by simple catalyst selection are discussed. Grubbs second-generation catalyst (G2) favors the formation of an alkylidene leading to the ROAlMP of (1). Grubbs first-generation catalyst (G1) favors vinylidene formation and prevents the homopolymerization of (1) even at elevated temperatures. Isolation and characterization of poly(1) by NMR analysis and MALDI-TOF confirms the generation of a well-defined polyallene that exhibits good thermal stability (T-D ca. 390 degrees C) and fluorescent properties. Ring-opening metathesis polymerization (ROMP) of a highly strained norbornene derivative (NBE-Pr-i) at 80 degrees C using the ruthenium vinylidene generated from (1) is also investigated. The discovery of ROAlMP allows for the simple access of well-defined polyallenes from commercially available catalysts and will ultimately guide structure-property determinations of polyallenes.

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《ACS Macro Letters》 |2021年第5期|共7页
作者
Neary William J.; Sun Yunyan; Moore Jeffrey S.;
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作者单位

Univ Illinois Beckman Inst Adv Sci &

Technol Urbana IL 61801 USA;

Univ Illinois Beckman Inst Adv Sci &

Technol Urbana IL 61801 USA;

Univ Illinois Beckman Inst Adv Sci &

Technol Urbana IL 61801 USA;

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正文语种 eng
中图分类有机化学;
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3. Synthesis, Structure, and Ring-opening Metathesis Polymerization of η5-Pentamethylcyclopentadienyl-（η5-exo-tricyclo 5.2.1.02＇6 deca-2,5,8-trien-6-yl） Iron [J] . ZHAO Xi, LI Bin, XU Shan-sheng, 高等学校化学研究：英文版 . 2009,第005期
4. Synthesis, Structure, and Ring-opening Metathesis Polymerization of η~5-Pentamethylcyclopentadienyl-(η~5-exo-tricyclo 5.2.1.0~(2,6)deca-2,5,8-trien-6-yl) Iron [J] . ZHAO Xi, LI Bin, XU Shan-sheng, 高等学校化学研究（英文版） . 2009,第005期
5. Cis-Selective Ring-Opening Metathesis Polymerization with Ruthenium Catalysts [J] . Benjamin K. Keitz, Alexey Fedorov, Robert H. Grubbs Journal of the American Chemical Society . 2012,第4期

机译：钌催化剂进行顺式选择开环复分解聚合
6. Synthesis of Highly Cis, Syndiotactic Polymers via Ring-Opening Metathesis Polymerization Using Ruthenium Metathesis Catalysts [J] . Lauren E. Rosebrugh, Vanessa M. Marx, Benjamin K. Keitz, Journal of the American Chemical Society . 2013,第27期

机译：钌复分解催化剂通过开环复分解聚合反应合成高顺式，间同规聚合物
7. Readily Accessible and Easily Modifiable Ru-Based Catalysts for Efficient and Z-Selective Ring-Opening Metathesis Polymerization and Ring-Opening/Cross-Metathesis [J] . R. Kashif M. Khan, Sebastian Torker, Amir H. Hoveyda Journal of the American Chemical Society . 2013,第28期

机译：易获得且易于修饰的Ru基催化剂，用于高效和Z选择性开环易位聚合和开环/交叉复分解
8. Living Ring-Opening Metathesis Polymerization of Doubly Polar Norbornene Derivatives Initiated by Ruthenium Carbene Complexes [C] . Yasushi Nishihara, Yoshiaki Inoue, Kentaro Takagi Symposium on Organometallic Chemistry . 2006

机译：由钌卡宾配合物引发双极降冰片烯衍生物的活性开环复分解聚合
9. Arm-First Synthesis of Star Polymers with Wedge Polymer Arms Using Ring-Opening Metathesis Polymerization and Bifunctional Crosslinkers [D] . Learsch, Robert. 2017

机译：使用开环复分解聚合和双官能交联剂的楔形聚合物臂的臂 - 首先合成星形聚合物。
10. Cis-Selective Ring-Opening Metathesis Polymerization with Ruthenium Catalysts [O] . Benjamin K. Keitz, Alexey Fedorov, Robert H. Grubbs -1

机译：顺选择性开环易位聚合与Ru催化剂
11. Selective Ring-Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation [O] . -1

机译：选择性环开口联合鼻定位：聚合或钌亚乙烯基形成
12. Well-Defined Redox-Active Polymers and Block Copolymers Prepared by Living Ring-Opening Metathesis Polymerization [R] . Albagli, D., Bazan, G., Wrighton, M. S., 1992

机译：通过活性开环易位聚合制备的定义明确的氧化还原活性聚合物和嵌段共聚物

Selective Ring-Opening Allene Metathesis: Polymerization or Ruthenium Vinylidene Formation

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