To further evince the key role of the open-shell Ir II configuration, we monitored the catalysis comparing our system to the Ir I precursor under conditions similar to those originally reported by Brookhart, Krogh-Jespersen and Goldman , that is, conducting the isomerization of 1octene employing the Ir I complex 1 as catalyst (1 mol%), at a considerably higher temperature (125 °C). The progression of the reaction was monitored using both 31 P{ 1 H} and 1 H NMR spectroscopy. Initially, the sole species detected was complex 1 (184.4 ppm by 31 P{ 1 H}), and upon heating at 125 °C, an instantaneous color shift from yellow to orange occurred. The 31 P{ 1 H} spectrum revealed the emergence of a new species characterized by a resonance at 180.2 ppm, presumed to be Ir(POCOP)(1-octene). The isomerization proceeded gradually, reaching around 25% conversion after 105 minutes (dashed line in Figure ). At this precise time, Ag[BAr F ] was added (one equivalent with respect to 1), resulting in a color change of the solution from orange to greenish-brown, while the 31 P{ 1 H} resonance fully disappears. By 1 H NMR spectroscopy we observed the reaction rate underwent a substantial increment, reaching around 85% in only 15 minutes (Figure ). Similarly, replicating the experiment in the presence of Ag[BAr F ] from the start of the reaction resulted in 86% conversion within 15 minutes at 125 °C, clearly demonstrating the boosting effect of silver as a one-electron oxidant to access the more active Ir II metalloradical. The isomerization of 1-hexene at 70 °C was equally monitored to examine the reaction profile of the Ir I catalyst 1 and the effect of adding the silver salt at a certain time (solid line in Figure ). Analogously, while only 5% isomerization was recorded for the Ir I precursor, the yield increased to around 45% after only 15 minutes upon addition of Ag[BAr F ].