A displacement-type fluorescent probe reveals active species in the coordinative polymerization of olefins†,Polymer Chemistry

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A displacement-type fluorescent probe reveals active species in the coordinative polymerization of olefins†
Polymer Chemistry ( IF 4.1 ) Pub Date : 2017-12-26 00:00:00 , DOI: 10.1039/c7py01915g
Chao Yu _{1,

2,

3,

4,

5} , Pengfei Zhang _{1,

2,

3,

4,

5} , Fei Gao _{1,

2,

3,

4,

5} , Shaowen Zhang _{1,

2,

3,

4,

5} , Xiaofang Li _{1,

2,

3,

4,

5}

Affiliation

The correct identification of active species is an important prerequisite to study the mechanism of coordinative polymerization of olefins, which can afford important theoretical guidance for the design and synthesis of new organometallic catalysts and high-performance polyolefin materials. However, it is very difficult to isolate and identify the catalytically active species generated from organometallic complex/activator/AlR₃ ternary systems during the coordinative polymerization of olefins. Herein, we present a new strategy to detect the catalytically active species in the coordination polymerization of olefins through the utilization of a displacement-type fluorescent probe containing an organometallic complex and an aluminum alkyl complex bearing the same chelating ligand. Using fluorescence spectroscopy and in situ¹H NMR spectroscopy, the truly active species is identified and a plausible mechanism is proposed, which provides new insights into the cis-1,4-polymerization of isoprene catalyzed by rare earth metal monoalkyl complex/activator/AlR₃ ternary systems.

中文翻译：

置换型荧光探针揭示了烯烃配位聚合中的活性物种†

正确识别活性物种是研究烯烃配位聚合机理的重要前提，它可以为新型有机金属催化剂和高性能聚烯烃材料的设计与合成提供重要的理论指导。然而，很难分离和鉴定由有机金属配合物/活化剂/ AlR ₃产生的催化活性物质。烯烃配位聚合过程中的三元体系。在这里，我们提出了一种新的策略，通过利用包含有机金属配合物和带有相同螯合配体的烷基铝配合物的置换型荧光探针来检测烯烃的配位聚合中的催化活性物质。使用荧光光谱和原位¹ H NMR光谱，鉴定了真正的活性物质，并提出了一个合理的机理，这为稀土金属单烷基络合物/活化剂/ AlR催化异戊二烯的顺式-1,4-聚合提供了新的见解。_3个三元系统。

更新日期：2017-12-26

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