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

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-η²:η²-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 σ_C–Li → s_Ni 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.

We disclose the actual octanuclear nature of the major compound from reacting Ni(COD)₂ and PhLi, assigned for more than four decades as ‘Li₃NiPh₃(solv)₃’. We provide a thorough bonding analysis and discuss its potential implications in catalysis.