Stoichiometric Formation of Open-Shell [PtAu24(SC2H4Ph)18]− via Spontaneous Electron Proportionation between [PtAu24(SC2H4Ph)18]2– and [PtAu24(SC2H4Ph)18]0

[PtAu24(SC2H4Ph)18]0 ([PtAu24]0) was fully and selectively converted to [PtAu24]−, having an open electronic structure with seven valence electrons, upon the addition of an equiamount of NaBH4. Stoichiometric production of [PtAu24]− by the reaction between an equal amount of [PtAu24]0 and [PtAu24]2– revealed that the above reaction proceeds via the spontaneous electron transfer (ET) from [PtAu24]2– nascently reduced by H–-mediated reduction to [PtAu24]0 remaining in the solution. Theoretical calculation suggested that the driving force of this novel ET reaction was the larger adiabatic electron affinity of [PtAu24]0 compared to that of [PtAu24]−, partly associated with reduction-induced relief of the Jahn–Teller strain. We propose that ET proceeds via the dimer complex of [PtAu24]2– and [PtAu24]0 formed through the aurophilic interaction between Au­(I) sites in the surface layer.