Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu30H18{E2P(OR)2}12] (E = S or Se; R = n Pr, i Pr or i Bu).

: Herein, we describe the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu30H18{S2P(O n Pr)2}12] (1H), fully characterized by various spectroscopic methods and single crystal X-ray diffraction. The X-ray structure of 1H reveals an unprecedented central Cu12 hollow icosahedron. Six faces of this icosahedron are capped by Cu3 triangles, the whole Cu30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S6 symmetry. The locations of the 18 hydrides in 1H was ascertained by a single crystal neutron diffraction. They are composed of three types: capping µ3-H, interstitial µ4-H (seesaw) and µ5-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1H NMR spectrum of 1H are in line with their coordination environment in the solid-state, retaining the S6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu30H18{Se2P(OR)2}12] (2H: R = i Pr 3H: R = i Bu) were synthesized from their sulfur relative 1Hvia ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. In addition, the reaction of 1H with [Pd(PPh3)2Cl2] in the presence of terminal alkynes led to the formation of new bimetallic Cu-Pd alloy clusters [PdCu14H2{S2P(O n Pr)2}6(C≡CR)6] (4: R = Ph; 5: R = C6H4F).