Heterobimetallic nickelates derived from Ni(0)-olefin complexes and polar organometallics were widely studied during the spawn of low-valent organonickel chemistry but remained dormant in the literature for several decades.1 We have recently demonstrated that nickelates are key intermediates in the Ni-catalysed cross-coupling of aryl ethers, prompting a renewed experimental and theoretical interest into these unique heterobimetallic complexes.2
In this talk, the synthesis and structures of homoleptic tri-lithium nickelates which can be readily accessed from Ni(COD)2 and lithium aryl-acetylides will be discussed.3 Complementary bonding analysis reveals that despite the apparent Li···Ni interactions observed in the solid-state, that these are repulsive in nature, whilst attractive London dispersion interactions are crucial for facilitating the isolation of such compounds. Mechanistic insights and applications of tri-lithium nickelates in catalytic cross-coupling reactions will also be discussed.4
- Jonas, C. Krüger. Angew. Chem. Int. Ed. Engl., 1980, 19, 520-537.
- (a) A. M. Borys, E. Hevia. Chem. Int. Ed., 2021, 60, 24659-24667. (b) H. Liang, A. Borys, E. Hevia, M. E. Perrin, P. A. Payard, J. Am. Chem. Soc. 2023, 145, 19989.
- (a) A. M. Borys, L. A. Malaspina, S. Grabowsky, E. Hevia. Chem. Int. Ed., 2022, 61, e202209797. (b) A. M. Borys, E. Hevia. Dalton Trans., 2023, 52, 2098-2105.
- M. Borys, L. Vedani, E. Hevia. manuscript in preparation