Catalysis with Pnictogen, Chalcogen, and Halogen Bonds. Issue 19 (20th March 2018)

• Record Type: Journal Article
• Authors: Benz, Sebastian; Poblador‐Bahamonde, Amalia I.; Low‐Ders, Nicolas; Matile, Stefan
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 19(2018)
• Page Start: 5408
• Page End: 5412
• Publication Date: 2018-03-20
• Subjects: anion binding -- catalysis -- chalcogen bonds -- halogen bonds -- pnictogen bonds; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201801452
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Halogen‐ and chalcogen‐based σ‐hole interactions have recently received increased interest in non‐covalent organocatalysis. However, the closely related pnictogen bonds have been neglected. In this study, we introduce conceptually simple, neutral, and monodentate pnictogen‐bonding catalysts. Solution and in silico binding studies, together with high catalytic activity in chloride abstraction reactions, yield compelling evidence for operational pnictogen bonds. The depth of the σ holes is easily varied with different substituents. Comparison with homologous halogen‐ and chalcogen‐bonding catalysts shows an increase in activity from main group VII to V and from row 3 to 5 in the periodic table. Pnictogen bonds from antimony thus emerged as by far the best among the elements covered, a finding that provides most intriguing perspectives for future applications in catalysis and beyond. Abstract : Antimony is the winner —perhaps surprisingly, perhaps not—of a comparative evaluation of the σ‐hole interactions of various pnictogen‐, chalcogen‐, and halogen‐bonding donors in anion binding and catalysis, with the strength decreasing according to Sb>Te>I>As>Se>Br, P. Catalysis with pnictogen bonds is reported for the first time.