结合光氧化还原和氢原子转移催化的无金属氢化硅烷化聚合,Journal of the American Chemical Society

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结合光氧化还原和氢原子转移催化的无金属氢化硅烷化聚合
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-11-05 , DOI: 10.1021/jacs.1c09263
Zhujun Huang ₁ , Zhe Chen ₁ , Yuan Jiang ₁ , Ning Li ₁ , Shicheng Yang ₁ , Guowei Wang ₁ , Xiangcheng Pan ₁

Affiliation

有机硅化合物和聚合物已广泛用作合成结构单元和功能材料。氢化硅烷化是合成有机硅化合物和聚合物的常用策略。尽管过渡金属催化的氢化硅烷化已经取得了很大进展，但二烯和双（硅烷）的无金属氢化硅烷化聚合，尤其是同时适用于富电子和缺电子二烯的聚合反应还很缺乏。在此，我们报道了一种使用有机光催化剂和氢原子转移 (HAT) 催化剂对富电子和缺电子二烯与双（硅烷）进行可见光驱动的无金属氢化硅烷化聚合。由于有机光催化剂 (4CzIPN) 和硫醇极性反转试剂 (HAT 1) 对 Si-H 键的选择性活化，我们实现了富电子二烯和双（硅烷）单体的良好控制的逐步生长氢化硅烷化聚合. 对于缺电子二烯，氢化硅烷化聚合和自聚合在 4CzIPN 和乙酰氯 (HAT 2) 的存在下同时发生，通过合理调整缺电子二烯的浓度和双（硅烷）和二烯的比例改变两种聚合反应的比例。范围广泛的双（硅烷）和二烯提供的聚碳硅烷具有高分子量、出色的热稳定性和可调节的结构。

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Metal-Free Hydrosilylation Polymerization by Merging Photoredox and Hydrogen Atom Transfer Catalysis

Organosilicon compounds and polymers have found wide applications as synthetic building blocks and functional materials. Hydrosilylation is a common strategy toward the synthesis of organosilicon compounds and polymers. Although transition-metal-catalyzed hydrosilylation has achieved great advances, the metal-free hydrosilylation polymerization of dienes and bis(silane)s, especially the one suitable for both electron-rich and electron-deficient dienes, is largely lacking. Herein, we report a visible-light-driven metal-free hydrosilylation polymerization of both electron-rich and electron-deficient dienes with bis(silane)s by using the organic photocatalyst and hydrogen atom transfer (HAT) catalyst. We achieved the well-controlled step-growth hydrosilylation polymerizations of the electron-rich diene and bis(silane) monomer due to the selective activation of Si–H bonds by the organic photocatalyst (4CzIPN) and the thiol polarity reversal reagent (HAT 1). For the electron-deficient dienes, hydrosilylation polymerization and self-polymerization occurred simultaneously in the presence of 4CzIPN and aceclidine (HAT 2), providing the opportunity to produce linear, hyperbranched, and network polymers by rationally tuning the concentration of electron-deficient dienes and the ratio of bis(silane)s and dienes to alter the proportion of the two polymerizations. A wide scope of bis(silane)s and dienes furnished polycarbosilanes with high molecular weight, excellent thermal stability, and tunable architectures.

更新日期：2021-11-17

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