Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations. Issue 9 (20th January 2017)

• Record Type: Journal Article
• Authors: Lipke, Mark C.; Liberman‐Martin, Allegra L.; Tilley, T. Don
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 9(2017)
• Page Start: 2260
• Page End: 2294
• Publication Date: 2017-01-20
• Subjects: catalysis -- hydrosilation -- main group elements -- σ complexes -- silylene; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201605198
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Hydrosilation reactions represent an important class of chemical transformations and there has been considerable recent interest in expanding the scope of these reactions by developing new catalysts. A major theme to emerge from these investigations is the development of catalysts with electrophilic character that transfer electrophilicity to silicon by Si‐H activation. This type of mechanism has been proposed for catalysts ranging from Group 4 transition metals to Group 15 main group species. Additionally, other electrophilic silicon species, such as silylene complexes and η 3 ‐H2 SiRR′ complexes, have been identified as intermediates in hydrosilation reactions. In this Review, different types of catalysts are compared to highlight the range of hydrosilation mechanisms that feature electrophilic silicon centers. The importance of these catalysts to the development of new hydrosilation reactions is also discussed. Abstract : On active duty : Catalysts based on elements from Groups 4–15 and that operate through electrophilic silane activation pathways are currently intensively investigated for hydrosilylations. This Review surveys these catalysts and describes several related mechanisms for electrophilic Si‐H activation (σ‐H‐Si coordination, M(H)2 =SiRR′ formation, η 3 ‐H2 SiRR′ binding).