In summary, our results emphasize the potential of mononuclear open-shell complexes to expand the efficiency and catalytic landscape of precious metals. Through the exploration of a small family of exotic Ir II complexes, we have demonstrated a significant enhancement in the catalytic activity compared to their well-known Ir I counterparts, achieving a remarkable 20-fold increase in activity for olefin isomerization reactions. This enhancement has been investigated by computational studies, supporting a novel Ir II /Ir IV catalytic cycle that is virtually analogous but kinetically favored compared to the traditional Ir I /Ir III pair. We have rationalized this unique catalytic enhancement by applying the ASM-EDA approach which suggests that the open-shell system kinetically favors the key initial C-H bond oxidative addition step mainly through stronger orbital and electrostatic interactions compared to the reduced Ir I analogue. Overall, this research underscores the significance of expanding the exploration of precious metal catalysts beyond conventional diamagnetic systems, paving the way for the design of more efficient and cost-effective catalysts.