Reaching odd-electron configurations that escape from the stability principles associated with closed-shell systems (i.e. 18-electron rule) often offers fruitful opportunities for boosting up reactivity. A well-known prototypical reaction is the substitution of metal carbonyls within isostructural compounds, where metalloradicals, as opposed to closed-shell analogues, exhibit markedly accelerated substitution rates. In a recent example, Stanley and coworkers successfully applied these principles to catalysis, employing a paramagnetic Co II catalyst that showcased a remarkable performance surpassing that of traditional Co I analogues in hydroformylation reactions. A thorough mechanistic investigation led to conclude that the additional positive charge at the cobalt center and the high-spin electronic configuration (via 19electron active species) played pivotal roles in this enhanced activity. However, this strategy remains mostly unexplored for precious 2 nd and 3 rd -row transition metals, likely because their odd-electron configurations are less accessible and have often been overseen or discarded due to practical reasons. While their potential involvement in catalytic cycles, especially in oxygenation chemistry, has been acknowledged, their precise roles remain ambiguous. In fact, the well-known catalytically active systems that present oddelectron counts are actually closed-shell bimetallic complexes exhibiting antiferromagnetic coupling and consequently diamagnetic character.( ) Hence, mononuclear metalloradicals with well-defined open-shell configurations hold a clear fundamental interest and could substantially enhance catalyst activity and thus reduce catalyst loadings, improving the overall cost efficiency of catalytic processes based on precious metals. Encouragingly, mononuclear open-shell precious metal complexes have already revealed a rich stoichiometric reactivity, participating in transformations such as H-H, C-H and C-C bond activations, (13) C-C and N-N coupling or oxygenation reactions (10b). Recently, we reported an Ir II metalloradical surpassing the dihydrogen activation capacity of its conventional Ir I counterpart by three orders of magnitude. This discovery prompted us to investigate the catalytic potential of monometallic Ir II complexes, posing a fundamental question: is it possible to develop a more efficient catalytic cycle revolving around the Ir II /Ir IV redox couple, diverging from the tenet of Ir I /Ir III or Ir III /Ir V pathways (Figure )? To address this question, herein we focus on the isomerization of olefins, a pivotal process in alkane metathesis, ( ) notorious for its demanding conditions when employing traditional Ir I complexes. ( )