[Cu13{S2CNnBu2}6(acetylide)4]+: A Two‐Electron Superatom. Issue 47 (26th October 2016)

• Record Type: Journal Article
• Authors: Chakrahari, Kiran Kumarvarma; Liao, Jian‐Hong; Kahlal, Samia; Liu, Yu‐Chiao; Chiang, Ming‐Hsi; Saillard, Jean‐Yves; Liu, C. W.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 47(2016)
• Page Start: 14704
• Page End: 14708
• Publication Date: 2016-10-26
• Subjects: centered cuboctahedra -- copper -- nanoclusters -- superatoms -- X-ray diffraction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201608609
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The first structurally characterized copper cluster with a Cu13 centered cuboctahedral arrangement, a model of the bulk copper fcc structure, was observed in [Cu13 (S2 CN n Bu2 )6 (C≡CR)4 ](PF6 ) (R=C(O)OMe, C6 H4 F) nanoclusters. Four of the eight triangular faces of the cuboctahedron are capped by acetylide groups in μ3 fashion, and each of the six square faces is bridged by a dithiolate ligand in μ2, μ2 fashion, which leads to a truncated tetrahedron of twelve sulfur atoms. DFT calculations are fully consistent with the description of these Cu13 clusters as two‐electron superatoms, that is, a [Cu13 ] 11+ core passivated by ten monoanionic ligands, with an a1 HOMO containing two 1S jellium electrons. Abstract : Just like in the metal : Cu13 clusters with a centered cuboctahedral unit, a model of the bulk Cu metal fcc structure, have been synthesized. The [Cu13 ] 11+ core can be described as a two‐electron superatom; four of the eight triangular faces are capped by acetylide groups, and each of the six square faces is bridged by a dithiolate ligand to yield ideal tetrahedral symmetry.