Recent advances in pincer-nickel catalyzed reactions.

Organometallic catalysts have played a key role in accomplishing numerous synthetically valuable organic transformations that are either otherwise not possible or inefficient. The use of precious, sparse and toxic 4d and 5d metals are an apparent downside of several such catalytic systems despite their immense success over the last several decades. The use of complexes containing Earth-abundant, inexpensive and less hazardous 3d metals, such as nickel, as catalysts for organic transformations has been an emerging field in recent times. In particular, the versatile nature of the corresponding pincer-metal complexes, which offers great control of their reactivity via countless variations, has garnered great interest among organometallic chemists who are looking for greener and cheaper alternatives. In this context, the current review attempts to provide a glimpse of recent developments in the chemistry of pincer-nickel catalyzed reactions. Notably, there have been examples of pincer-nickel catalyzed reactions involving two electron changes via purely organometallic mechanisms that are strikingly similar to those observed with heavier Pd and Pt analogues. On the other hand, there have been distinct differences where the pincer-nickel complexes catalyze single-electron radical reactions. The applicability of pincer-nickel complexes in catalyzing cross-coupling reactions, oxidation reactions, (de)hydrogenation reactions, dehydrogenative coupling, hydrosilylation, hydroboration, C-H activation and carbon dioxide functionalization has been reviewed here from synthesis and mechanistic points of view. The flurry of global pincer-nickel related activities offer promising avenues in catalyzing synthetically valuable organic transformations.