Formation of XPhos-Ligated Palladium(0) Complexes and Reactivity in Oxidative Additions

Understanding the nature of the intermediate species operating within a palladium catalytic cycle is crucial for developing efficient cross-coupling reactions. Even though the XPhos/Pd(OAc)₂ catalytic system has found numerous applications, the nature of the active catalytic species remains elusive. A Pd⁰ complex ligated to XPhos has been detected and characterized in situ for the first time using cyclic voltammetry and NMR techniques. In the presence of XPhos, Pd(OAc)₂ initially associates with the ligand to form a complex in solution, which has been characterized as Pd^II (OAc)₂ (XPhos). This Pd^II center is then reduced to the Pd⁰ (XPhos)₂ species by an intramolecular process. This study also sheds light on the formation of Pd^I -Pd^I dimers. Finally, a kinetic study probes a dissociative mechanism for the oxidative addition with aryl halides involving Pd⁰ (XPhos) as the reactive species in equilibrium with the unreactive Pd⁰ (XPhos)₂ . Remarkably, the reportedly poorly reactive PhCl reacts at room temperature in the oxidative addition, which confirms the crucial role of the XPhos ligand in the activation of aryl chlorides.