Phosphinothiolates as Ligands for Polyhydrido Copper Nanoclusters

The reaction of [CuI(HSC6H4PPh2)](2) with NaBH4 in CH2Cl2/EtOH led to air- and moisture-stable copper hydride nanoparticles (CuNPs) containing phosphinothiolates as new ligands, one of which was isolated by crystallization. The X-ray crystal structure of [Cu18H7L10I] (L=S-(C6H4)PPh2) shows unprecedented features in its 28-atom framework (18Cu and 10S atoms). Seven hydrogen atoms, in hydride form, are needed for charge balance and were located by density functional theory methods. H-2 was released from the copper hydride nanoparticles by thermolysis and visible light irradiation.