Issue 18, 2022

Unmasking the constitution and bonding of the proposed lithium nickelate “Li3NiPh3(solv)3”: revealing the hidden C6H4 ligand

Abstract

More than four decades ago, a complex identified as the planar homoleptic lithium nickelate “Li3NiPh3(solv)3” was reported by Taube and co-workers. This and subsequent reports involving this complex have lain dormant since; however, the absence of an X-ray diffraction structure leaves questions as to the nature of the Ni–PhLi bonding and the coordination geometry at Ni. By systematically evaluating the reactivity of Ni(COD)2 with PhLi under different conditions, we have found that this classical molecule is instead a unique octanuclear complex, [{Li3(solv)2Ph3Ni}2(μ-η22-C6H4)] (5). This is supported by X-ray crystallography and solution-state NMR studies. A theoretical bonding analysis from NBO, QTAIM, and ELI perspectives reveals extreme back-bonding to the bridging C6H4 ligand resulting in dimetallabicyclobutane character, the lack of a Ni–Ni bond, and pronounced σ-bonding between the phenyl carbanions and nickel, including a weak σC–Li → sNi interaction with the C–Li bond acting as a σ-donor. Employing PhNa led to the isolation of [Na2(solv)3Ph2NiCOD]2 (7) and [Na2(solv)3Ph2(NaC8H11)Ni(COD)]2 (8), which lack the benzyne-derived ligand. These findings provide new insights into the synthesis, structure, bonding and reactivity of heterobimetallic nickelates, whose prevalence in organonickel chemistry and catalysis is likely greater than previously believed.

Graphical abstract: Unmasking the constitution and bonding of the proposed lithium nickelate “Li3NiPh3(solv)3”: revealing the hidden C6H4 ligand

Supplementary files

Article information

Article type
Edge Article
Submitted
01 Marts 2022
Accepted
08 Apr. 2022
First published
11 Apr. 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 5268-5276

Unmasking the constitution and bonding of the proposed lithium nickelate “Li3NiPh3(solv)3”: revealing the hidden C6H4 ligand

R. J. Somerville, A. M. Borys, M. Perez-Jimenez, A. Nova, D. Balcells, L. A. Malaspina, S. Grabowsky, E. Carmona, E. Hevia and J. Campos, Chem. Sci., 2022, 13, 5268 DOI: 10.1039/D2SC01244H

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