Regioselective Isomerization of Terminal Alkenes Catalyzed by a PC(sp ³ )Pincer Complex with a Hemilabile Pendant Arm

We describe an efficient protocol for the regioselective isomerization of terminal alkenes employing a previously described bifunctional Ir‐based PC(sp3)complex (4) possessing a hemilabile sidearm. The isomerization, catalyzed by 4, results in a one‐step shift of the double bond in good to excellent selectivity, and good yield. Our mechanistic studies revealed that the reaction is driven by the stepwise migratory insertion of Ir−H species into the terminal double bond/β‐H elimination events. However, the selectivity of the reaction is controlled by dissociation of the hemilabile sidearm, which acts as a selector, favoring less sterically hindered substrates such as terminal alkenes; importantly, it prevents recombination and further isomerization of the internal ones.