[Cu 13 {S 2 CN n Bu 2 } 6 (acetylide) 4 ] + : A Two‐Electron Superatom

The first structurally characterized copper cluster with a Cu 13 centered cuboctahedral arrangement, a model of the bulk copper fcc structure, was observed in [Cu 13 (S 2 CN n Bu 2 ) 6 (C≡CR) 4 ](PF 6 ) (R=C(O)OMe, C 6 H 4 F) nanoclusters. Four of the eight triangular faces of the cuboctahedron are capped by acetylide groups in μ 3  fashion, and each of the six square faces is bridged by a dithiolate ligand in μ 2 ,μ 2 fashion, which leads to a truncated tetrahedron of twelve sulfur atoms. DFT calculations are fully consistent with the description of these Cu 13 clusters as two‐electron superatoms, that is, a [Cu 13 ] 11+ core passivated by ten monoanionic ligands, with an a 1 HOMO containing two 1S jellium electrons.