A different polynorbornene backbone by combination of two polymer growth pathways: vinylic addition and ring opening via β-C elimination,Chemical Science

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A different polynorbornene backbone by combination of two polymer growth pathways: vinylic addition and ring opening via β-C elimination
Chemical Science ( IF 7.6 ) Pub Date : 2022-01-20 , DOI: 10.1039/d1sc07028b
Ignacio Pérez-Ortega ₁ , Ana C Albéniz ₁

Affiliation

A new polynorbornene skeleton has been found that contains bicyclic norbornane units and cyclohexenyl methyl linkages. The polymers have been synthesized using a nickel catalyst in the presence of a controlled amount of ligands with low or moderate coordination ability. The backbone structure is the result of a vinylic addition polymerization, via sequential insertions of norbornene into a Ni–C bond (bicyclic units) combined with an unusual ring opening of the norbornene structure by a β-C elimination (cyclohexenyl methyl units) to give a new Ni–C(alkyl) bond that continues the polymerization. The ring opening events are favored when the rate of propagation of the vinylic addition polymerization decreases, and this can be modulated by making the coordination of norbornene to the metal center less favorable using additional ligands.

中文翻译：

通过两种聚合物生长途径的组合形成不同的聚降冰片烯主链：乙烯基加成和通过 β-C 消除的开环

已经发现了一种新的聚降冰片烯骨架，它包含双环降冰片烷单元和环己烯基甲基键。该聚合物是在控制量的具有低或中等配位能力的配体存在下使用镍催化剂合成的。主链结构是乙烯加成聚合的结果，通过降冰片烯连续插入 Ni-C 键（双环单元）与降冰片烯结构的异常开环通过 β-C 消除（环己烯基甲基单元）相结合，形成新的 Ni-C（烷基）键，继续聚合. 当乙烯基加成聚合的传播速率降低时，开环事件是有利的，这可以通过使用额外的配体使降冰片烯与金属中心的配位不太有利来调节。

更新日期：2022-01-20

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