Assessing Coordination of Organic π-Acceptors to Alkali-Metal Nickelates.

Nickel olefin complexes have served as ubiquitous precursors in nickel chemistry ever since their discovery. One class of compounds derived from these precursors is low valent nickelate complexes. While their role as key intermediates in challenging cross-coupling reactions has recently been confirmed, knowledge regarding the coordination preferences of these complexes, in particular when extended to π-systems, is still very limited. Herein we present a summary of our most important findings from the investigation of the coordination of a series of organic π-acceptors to low valent alkali-metal nickelate complexes. This includes the coordination of polyaromatic molecules such as anthracene or coronene. Extending these studies to biphenylene has uncovered the ability of these heterobimetallic complexes to mediate C-C bond oxidative addition processes, where the nature of the alkali-metal plays an important role in influencing the rate of these activations.