[Cu-32(H)(20){S2P(OiPr)(2)}(12)]: The Largest Number of Hydrides Recorded in a Molecular Nanocluster by Neutron Diffraction

Abstract

An air- and moisture-stable nanoscale polyhydrido copper cluster [Cu-32(H)(20){S2P(OiPr)(2)}(12)] (1(H)) was synthesized and structurally characterized. The molecular structure of 1(H) exhibits a hexacapped pseudo-rhombohedral core of 14 Cu atoms sandwiched between two nestlike triangular cupola fragments of (2x9) Cu atoms in an elongated triangular gyrobicupola polyhedron. The discrete Cu-32 cluster is stabilized by 12 dithiophosphate ligands and a record number of 20 hydride ligands, which were found by high-resolution neutron diffraction to exhibit tri-, tetra-, and pentacoordinated hydrides in capping and interstitial modes. This result was further supported by a density functional theory investigation on the simplified model [Cu-32(H)(20)(S2PH2)(12)].