[Ni₈(CN^tBu)₁₂][Cl]: A nickel isocyanide nanocluster with a folded nanosheet structure

The reaction of 1.75 equiv of ^tBuNC with Ni(1,5-COD)₂, followed by crystallization from benzene/pentane, resulted in the isolation of [Ni₈(CN^tBu)₁₂][Cl] (2) in low yields. Similarly, the reaction of Ni(1,5-COD)₂ with 0.6 equiv of [Ni(CN^tBu)₄], followed by addition of 0.08 equiv of I₂, resulted in the formation of [Ni₈(CN^tBu)₁₂][I] (3), which could be isolated in 52% yield after work-up. Both 2 and 3 adopt folded nanosheet structures in the solid state, characterized by two symmetry-related planar Ni₄ arrays, six terminally bound ^tBuNC ligands, and six ^tBuNC ligands that adopt bridging coordination modes. The metrical parameters of the six bridging ^tBuNC ligands suggest that they have been reduced to their [^tBuNC]^2- form. In contrast to the nanosheet structures observed for 2 and 3, gas phase Ni₈ is predicted to feature a compact bisdisphenoid ground state structure. The strikingly different structural outcomes reveal the profound structural changes that can occur upon addition of ligands to bare metal clusters. Ultimately, the characterization of 2 and 3 will enable more accurate structural predictions of ligand-protected nanoclusters in the future.