Ligand-Metal Cooperation in PCP Pincer Complexes: Rational Design and Catalytic Activity in Acceptorless Dehydrogenation of Alcohols

A helping hand: The dibenzobarrelene‐based PC sp 3P pincer complex 1 was designed as a bifunctional catalyst for the acceptorless dehydrogenation of alcohols. The mechanism of the H2 release involves interaction between the hydride ligand and the acidic sidearm in the intermediate 2 (red O, yellow Cl, green P, blue Ir). The feasibility of the complete catalytic cycle was studied using a stoichiometric model and the reaction was subsequently realized in a catalytic fashion.