Unmasking the constitution and bonding of the proposed lithium nickelate "Li(3)NiPh(3)(solv)(3)": revealing the hidden C(6)H(4) ligand.

More than four decades ago, a complex identified as the planar homoleptic lithium nickelate "Li(3)NiPh(3)(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, [{Li(3)(solv)(2)Ph(3)Ni}(2)(μ-η(2):η(2)-C(6)H(4))] (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 C(6)H(4) 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 [Na(2)(solv)(3)Ph(2)NiCOD](2) (7) and [Na(2)(solv)(3)Ph(2)(NaC(8)H(11))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.