[Cu-13{(S2CNBu2)-Bu-n}(6)(acetylide)(4)](+): A Two-Electron Superatom

摘要

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((S2CNBu2)-Bu-n)(6)(C CR)(4)](PF6) (R = C(O)OMe, C6H4F) nano-clusters. Four of the eight triangular faces of the cuboctahedron are capped by acetylide groups in mu(3) fashion, and each of the six square faces is bridged by a dithiolate ligand in mu(2),mu(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.