Towards Hexagonal Planar Nickel: A Dispersion-Stabilised Tri-Lithium Nickelate.

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

[img] Text
Angew_Chem_Int_Ed_-_2022_-_Borys_-_Towards_Hexagonal_Planar_Nickel_A_Dispersion_Stabilised_Tri_Lithium_Nickelate.pdf - Accepted Version
Restricted to registered users only until 3 August 2023.
Available under License Publisher holds Copyright.

Download (9MB) | Request a copy

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)

Division/Institute:

08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Borys-Smith, Andryj Machaelo; Malaspina, Lorraine; Grabowsky, Simon and 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:

05 Dec 2022 16:22

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

Actions (login required)

Edit item Edit item
Provide Feedback