Cooperative Effects in Switchable Catalysis: Enhancing Double‐Click Reaction Yield of Symmetrical Rotaxanes. Issue 37 (7th August 2021)

• Record Type: Journal Article
• Authors: Ghosh, Amit; Paul, Indrajit; Schmittel, Michael
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 37(2021)
• Page Start: 20558
• Page End: 20562
• Publication Date: 2021-08-07
• Subjects: catalysis -- click reaction -- cooperativity -- rotaxane -- supramolecular switch; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202108269
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Reversible switching between the closed cyclic dimeric assembly [Cu2 (1 )2 ] 2+ (OFF state) and the extended dimeric homoleptic complex [FeCu2 (1 )2 ] 4+ (ON State) by addition/removal of Fe 2+ triggered catalysis of a double‐click reaction and high yield preparation of [2]rotaxanes. Mechanistic and computational studies provide valuable general insight for double‐click strategies by revealing cooperative effects in the second cycloaddition step due to a distance‐tolerant preorganization of the first‐click product by the two copper(I)‐loaded phenanthroline subunits of [FeCu2 (1 )2 ] 4+ . Abstract : Like an eagle spreading its wings wide, the closed structure opens its hidden catalytic sites upon addition of an iron trigger thus furnishing a cavity for a double‐click conversion toward rotaxanes. Surprisingly, a close distance match is not needed for double activation.