biostudies-literatureUnknown16(48)Cobb JRECation-switchable catalysis is a promising strategy for modulating reaction rates or selectivity using external stimuli, with potential applications including polymer synthesis and tandem catalysis. This study establishes a deeper understanding of the mechanistic origins of cation rate promotion in systems where a hemilabile crown ether affixed to the catalyst serves as a cation receptor site, which in turn enables reactivity extensions of this platform to introduce cation-switchable alkene hydrogenation. The mechanistic study hinges on the synthesis of two previously unreported iridium(iii) complexes, bearing either bis(2-methoxyethyl)amine or diethylamine groups, which could be compared in catalysis with and without cation promoters. Only the catalyst containing a crown ether exhibits swChemical science23330-23341https://www.ebi.ac.uk/biostudies/studies/S-EPMC12593864biostudies-literatureCation-switchable transposition and hydrogenation of alkenes <i>via</i> interconnected reaction mechanisms.PMC12593864Yoo CBhattacharya SMiller AJMCobb JREDodge HMChen CHPerez Galarza EDStuart ZEfalseCation-switchable transposition and hydrogenation of alkenes <i>via</i> interconnected reaction mechanisms.Cation-switchable catalysis is a promising strategy for modulating reaction rates or selectivity using external stimuli, with potential applications including polymer synthesis and tandem catalysis. This study establishes a deeper understanding of the mechanistic origins of cation rate promotion in systems where a hemilabile crown ether affixed to the catalyst serves as a cation receptor site, which in turn enables reactivity extensions of this platform to introduce cation-switchable alkene hydrogenation. The mechanistic study hinges on the synthesis of two previously unreported iridium(iii) complexes, bearing either bis(2-methoxyethyl)amine or diethylamine groups, which could be compared in catalysis with and without cation promoters. Only the catalyst containing a crown ether exhibits sw2025-01-01T00:00:00Z2025 Dec2026-07-15T06:43:40.167Z2026-06-30T03:22:52.383ZS-EPMC125938644121028610.1039/d5sc06143a