AB- Versus AA+BB-Suzuki Polycondensation: A Palladium/Tris(tert-butyl)phosphine Catalyst Can Outperform Conventional Catalysts.
AB- Versus AA+BB-Suzuki Polycondensation: A Palladium/Tris(tert-butyl)phosphine Catalyst Can Outperform Conventional Catalysts.
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DOI：
10.1002/marc.201900521
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发表时间：
2019-12
影响因子：
4.6
通讯作者：
Kenan Zhang;R. Tkachov;Kristina Ditte;N. Kiriy;A. Kiriy;Brigitte Vot
中科院分区：
文献类型：
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作者：
Kenan Zhang;R. Tkachov;Kristina Ditte;N. Kiriy;A. Kiriy;Brigitte Vot
具有大体积富电子配体的Pd/Pt-Bu 3催化剂在AB型亚芳基基单体（例如一些取代的芴、咔唑和亚苯基）的Suzuki缩聚中显著优于常规的“逐步生长催化剂”Pd（PPh 3）4和Pd（Po-Tol 3）3。在AA+BB缩聚中，Pd/Pt-Bu 3与有机碱Et 4 NOH组合在均相反应条件下也表现得更好。讨论了Pd/Pt-Bu 3催化剂的上级性能，包括其在氧化加成反应中较高的反应活性和分子内催化剂转移的固有优势，这是连接AB缩聚催化循环的关键步骤。这些发现被应用于合成一种基于咔唑的共聚物，该共聚物被设计用作溶液处理有机发光二极管中的空穴导体。
A Pd/Pt-Bu3 catalyst having bulky, electron-rich ligands significantly outperforms conventional "step-growth catalysts" Pd(PPh3 )4 and Pd(Po-Tol3 )3 in the Suzuki polycondensation of the AB-type arylene-based monomers, such as some of the substituted fluorenes, carbazoles, and phenylenes. In the AA+BB polycondensation, Pd/Pt-Bu3 also performs better under homogeneous reaction conditions, in combination with the organic base Et4 NOH. The superior performance of Pd/Pt-Bu3 is discussed in terms of its higher reactivity in the oxidative addition step and inherent advantages of the intramolecular catalyst transfer, which is a key step joining catalytic cycles of the AB-polycondensation. These findings are applied to the synthesis of a carbazole-based copolymer designed for the use as a hole conductor in solution-processed organic light-emitting diodes.