Silanes are important in chemistry and material science. The self‐redistribution of HSiCl3is 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 Ni0‐NiII‐NiIVcatalytic cycle.
Nickel‐Catalyzed Cross‐Redistribution between Hydrosilanes and Silacyclobutanes
Silanes are important in chemistry and material science. The self‐redistribution of HSiCl3is 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 Ni0‐NiII‐NiIVcatalytic cycle.
more » « less- NSF-PAR ID:
- 10379754
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 61
- Issue:
- 50
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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