Observable but Not Isolable: The RhAu₂₄ (PET)₁₈¹⁺ Nanocluster

The synthesis and characterization of RhAu₂₄ (PET)₁₈ (PET = 2-phenylethanethiol) is described. The cluster is cosynthesized with Au₂₅ (PET)₁₈ and rhodium thiolates in a coreduction of RhCl₃ , HAuCl₄ , and PET. Rapid decomposition of RhAu₂₄ (PET)₁₈ occurs when purified from the other reaction products, precluding the study of isolated cluster. Mixtures containing RhAu₂₄ (PET)₁₈ , Au₂₅ (PET)₁₈ , and rhodium thiolates are therefore characterized. Mass spectrometry, X-ray photoelectron spectroscopy, and chromatography methods suggest a combination of charge-charge and metallophilic interactions among Au₂₅ (PET)₁₈^1- , rhodium thiolates and RhAu₂₄ (PET)₁₈ resulting in stabilization of RhAu₂₄ (PET)₁₈ . The charge of RhAu₂₄ (PET)₁₈ is assigned as 1+ on the basis of its stoichiometric 1:1 presence with anionic Au₂₅ (PET)₁₈ , and its stability is contextualized within the superatom electron counting rules. This analysis concludes that the Rh atom absorbs one superatomic electron to close its d-shell, giving RhAu₂₄ (PET)₁₈¹⁺ a superatomic electron configuration of 1S² 1P⁴ . Overall, an updated framework for rationalizing open d-shell heterometal dopant electronics in thiolated gold nanoclusters emerges.