[Ag21{S2P(OiPr)2}12] +: An Eight‐Electron Superatom.

The [Ag21{S2P(OiPr)2}12] (PF6) nanocluster is prepared by combining a THF solution of NH4[S2P(OiPr)2] and NaBH4 with a THF solution of Ag(MeCN)4PF6 (Schlenk tube, -20 °C, 4 h) followed by warming to 25 °C and multistep isolation.