Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 39, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202209797
Keywords
Complementary Bonding Analysis; London Dispersion; Nickel; Organolithium; Transition-Metal Complexes
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Funding
- Swiss National Science Foundation (SNSF) within the REquip programme [206021_177033]
- Universitat Bern
- SNSF [188573]
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Through the study of the family of organonickelate complexes, we have discovered a rare class of low-valent transition metal complexes with repulsive Ni-Li interactions, forming tri-coordinated structures. Additionally, London dispersion forces play a crucial role in the stabilization and isolation of these complexes.
Advancing the understanding of lithum nickelate complexes, here we report a family of homoleptic organonickelate complexes obtained by reacting Ni(COD)(2) and 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.
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