Nickel‐Catalyzed Cross‐Redistribution between Hydrosilanes and Silacyclobutanes. Issue 50 (10th November 2022)

• Record Type: Journal Article
• Authors: Chen, Shaowei; He, Xiaoqian; Jin, Chenyu; Zhang, Weilu; Yang, Yuxi; Liu, Shanshan; Lan, Yu; Houk, Kendall N.; Shen, Xiao
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 50(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-11-10
• Subjects: Cross-Redistribution -- Enthalpy-Driven -- Silacyclobutanes -- Nickel Catalysis -- Silane; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202213431
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Silanes are important in chemistry and material science. The self‐redistribution of HSiCl3 is an industrial process to prepare SiH4, which is widely used in electronics and automobile industries. However, selective silane cross‐redistribution to prepare advanced silanes is challenging. We now report an enthalpy‐driven silane cross‐redistribution to access bis‐silanes that contain two different types of Si−H bonds in the same molecule. Compared with entropy‐driven reactions, the enthalpy‐driven reaction shows high regioselectivity, broad substrate scope (62 examples) and high atom economy. Our combined experimental and computational study indicates that the reaction proceeds through a Ni 0 ‐Ni II ‐Ni IV catalytic cycle. Abstract : A nickel‐catalyzed silane cross‐redistribution reaction was developed for the synthesis of bis‐silanes. The reaction is driven by enthalpy but not entropy, and the reaction is atom economical, without formation of gaseous silane side product. The reaction has broad substrate scope. This combined computational and experimental study shows that the reaction proceeds through a Ni 0 ‐Ni II ‐Ni IV catalytic cycle.