Borys-Smith, Andryj MachaeloAndryj MachaeloBorys-SmithMalaspina, LorraineLorraineMalaspina0000-0002-8281-4264Grabowsky, SimonSimonGrabowsky0000-0002-3377-9474Hevia Freire, EvaEvaHevia Freire0000-0002-3998-75062024-10-112024-10-112022-09-26https://boris-portal.unibe.ch/handle/20.500.12422/86503Advancing the understanding of lithum nickelate complexes, here we report a family of homoleptic organonickelate complexes obtained by reacting Ni(COD)2and lithium aryl-acetylides in the presence of the bidentate donor TMEDA. These compounds represent rare examples of low-valent transition-metals supported solely by organolithium ligands. Whilst the solid-state structures indicate a hexagonal planar geometry around Ni(0) with Ni-Li bonds, bonding analysis via QTAIM, NCI, NBO and ELI methods reveals that the Ni-Li interactions are repulsive in nature, characterising these complexes as tri-coordinated. London dispersion forces between TMEDA and the organic substituents on nickel are found to play a crucial role in the stabilisation and thus isolation of these complexes. Preliminary reactivity studies demonstrate that the homoleptic lithium nickelates undergo stoichiometric cross-coupling with PhI to give dinickel clusters containing both anionic acetylide and neutral alkyne ligands.enLondon dispersion complementary bonding analysis nickel organolithium transition-metal complexes500 - Science::570 - Life sciences; biology500 - Science::540 - Chemistryarticle10.48350/1717273592121310.1002/anie.202209797