Shell engineering of an atomically precise PdH-doped Cu nanocluster

Abstract A bimetallic cluster [PdHCu12{S2P(OiPr)2}6(C2Ph)3(S)] denoted as PdHCu12S was prepared by controlled exfoliation of [PdH2Cu14{S2P(OiPr)2}6(C2Ph)6] denoted as PdH2Cu14 with HTAF. Single-crystal X-ray diffraction analysis of the synthesized cluster revealed that it has a PdH-centered cuboctahedral Cu12 core protected by 6 dithiophosphates, a sulfide, and 3 alkynyl ligands. The substitution of the C2Ph− ligand in the linear H-Pd-C2Ph unit of PdHCu12C with a sulfide ligand altered the function of the interstitial hydride from electron-donating to electron-withdrawing.