Loading…
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,...
Saved in:
Published in: | Journal of the American Chemical Society 2021-11, Vol.143 (45), p.19167-19177 |
---|---|
Main Authors: | , , , , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
Summary: | 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. |
---|---|
ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/jacs.1c09263 |