Borys, Andryj M; Malaspina, Lorraine A; Grabowsky, Simon; Hevia Freire, Eva (2022). Towards Hexagonal Planar Nickel: A Dispersion-Stabilised Tri-Lithium Nickelate. Angewandte Chemie (International ed.), 61(39), e202209797. Wiley-VCH 10.1002/anie.202209797
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Angew_Chem_Int_Ed_-_2022_-_Borys_-_Towards_Hexagonal_Planar_Nickel_A_Dispersion_Stabilised_Tri_Lithium_Nickelate.pdf - Accepted Version Available under License Publisher holds Copyright. Download (9MB) | Preview |
Advancing 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.
Item Type: |
Journal Article (Original Article) |
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Division/Institute: |
08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP) |
UniBE Contributor: |
Borys-Smith, Andryj Machaelo, Malaspina, Lorraine, Grabowsky, Simon, Hevia Freire, Eva |
Subjects: |
500 Science > 570 Life sciences; biology 500 Science > 540 Chemistry |
ISSN: |
1433-7851 |
Publisher: |
Wiley-VCH |
Language: |
English |
Submitter: |
Pubmed Import |
Date Deposited: |
05 Aug 2022 09:25 |
Last Modified: |
04 Aug 2023 00:25 |
Publisher DOI: |
10.1002/anie.202209797 |
PubMed ID: |
35921213 |
Uncontrolled Keywords: |
London dispersion complementary bonding analysis nickel organolithium transition-metal complexes |
BORIS DOI: |
10.48350/171727 |
URI: |
https://boris.unibe.ch/id/eprint/171727 |
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