New ligand-exchange reactions are reported for thiolate- and acetylide-protected gold nanoclusters, which are rationalized through bond strengths and enthalpy arguments.

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)181−, 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 1S21P4. Overall, an updated framework for rationalizing open d‐shell heterometal dopant electronics in thiolated gold nanoclusters emerges.

The synthesis and characterization of an Au20(PET)15(DG)2 (PET=phenylethane thiol; DG=Diglyme) cluster is reported. Mass spectrometry reveals this as the first diglyme ligated cluster where diglyme ligands survive ionization into the...