UC Santa Barbara

The reaction of [Ni(1,5-COD)₂] (1.0 equiv), PEt₃ (0.04 equiv), SePEt₃ (0.52 equiv), and [NiCl₂(PEt₃)₂] (0.07 equiv) in a mixture of toluene and THF results in the formation of [Ni₂₃Se₁₂Cl₃(PEt₃)₁₀] (1), which can be isolated in moderate yield after workup. Complex 1 was characterized by NMR spectroscopy, ESI-MS, and X-ray crystallography. This open-shell nanocluster features a central [Ni₁₃]⁷⁺ anticuboctahedral kernel, which is encapsulated by a [Ni₁₀(μ-Se)₉Cl₃]^- shell, along with ten PEt₃ ligands and three (μ₄-Se)^2- ligands. On the basis of our spectroscopic and crystallographic analysis, coupled with in situ spectroscopic monitoring, we believe that the previously reported nanocluster, [Ni₂₃Se₁₂(PEt₃)₁₃], is actually better formulated as [Ni₂₃Se₁₂Cl₃(PEt₃)₁₀].