Abstract A series of Ir–PCP pincer precatalysts [(7–6–7-R PCP) Ir (H)(Cl)] and [(7–6–7-Ar PCP) Ir (H)(Cl)(MeCN)] bearing a novel “7–6–7” fused-ring skeleton have been synthesized based upon the postulate that the catalytic species would have durability due to their rather rigid structure and high activity owing to the low but sufficient flexibility of their backbones, which are not completely fixed. Treatment of these precatalysts with NaOtBu gave rise to ...