Recent Developments in the Field of Air‐Stable Nickel(0) Precatalysts for Cross‐Coupling Reactions

The development of bench‐stable Ni(0) precatalysts marks a significant turning point in nickel catalysis, offering a practical path beyond the long‐standing dependence on air‐sensitive Ni sources, such as Ni(COD) 2 (COD = cycloocta‐1,5‐diene). These next‐generation complexes provide direct access to the catalytically active Ni(0) oxidation state, while remaining stable to air and moisture. This simplifies their handling and expands their potential for both academic and industrial applications. In this context, two main synthetic strategies dominate: ligand exchange from Ni(COD) 2 and reduction of Ni(II) salts using chemical or electrochemical methods. The success of bench‐stable Ni(0) complexes relies on a targeted ligand design, employing strong π‐acceptors and donors, such as electron‐deficient dienes, carbenes, and fluorophosphines, to balance catalyst stability with a high catalytic activity. At the same time, the ligand environment must allow a facile exchange, without the released ligand inhibiting the metal centre through re‐coordination. Beyond their practical advantages, these systems are compatible with high‐throughput and data‐driven discoveries, accelerating the development of C–C and C–heteroatom cross‐coupling reactions. As nickel catalysis continues, bench‐stable Ni(0) systems are thought to open up a new generation of sustainable and scalable homogeneous catalysts for many organic transformations.